KR20110109938A - Soluble polyfunctional (meth)acrylic ester copolymer, and method for production thereof, curable resin composition and cured product - Google Patents
Soluble polyfunctional (meth)acrylic ester copolymer, and method for production thereof, curable resin composition and cured product Download PDFInfo
- Publication number
- KR20110109938A KR20110109938A KR1020110027549A KR20110027549A KR20110109938A KR 20110109938 A KR20110109938 A KR 20110109938A KR 1020110027549 A KR1020110027549 A KR 1020110027549A KR 20110027549 A KR20110027549 A KR 20110027549A KR 20110109938 A KR20110109938 A KR 20110109938A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylic acid
- acid ester
- acrylate
- copolymer
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 98
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 83
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 44
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims abstract description 34
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 25
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 73
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000013329 compounding Methods 0.000 claims description 20
- 239000010419 fine particle Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004386 diacrylate group Chemical group 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 claims description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical group C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 8
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 4
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- TUAJZTAVXLCEGA-UHFFFAOYSA-N 1-hydroxyethyl prop-2-enoate Chemical compound CC(O)OC(=O)C=C TUAJZTAVXLCEGA-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 46
- 238000002834 transmittance Methods 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 11
- -1 ethylene, substituted ethylene, propylene, substituted propylene, styrene Chemical class 0.000 description 34
- 239000002904 solvent Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- 239000003960 organic solvent Substances 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 21
- 239000000523 sample Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000008119 colloidal silica Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000012986 chain transfer agent Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 239000011147 inorganic material Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- NBTXFNJPFOORGI-UHFFFAOYSA-N 2-ethenoxyethyl prop-2-enoate Chemical compound C=COCCOC(=O)C=C NBTXFNJPFOORGI-UHFFFAOYSA-N 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- GMAPHLQQWWDCHP-UHFFFAOYSA-N (4-methyl-1-phenylpent-1-enyl)benzene Chemical compound C=1C=CC=CC=1C(=CCC(C)C)C1=CC=CC=C1 GMAPHLQQWWDCHP-UHFFFAOYSA-N 0.000 description 2
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- YVAACGXAZGGQSM-UHFFFAOYSA-N 2,2-dimethylpropaneperoxoic acid Chemical compound CC(C)(C)C(=O)OO YVAACGXAZGGQSM-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- MMNIKCLHZKAPGA-UHFFFAOYSA-N bis(2-propan-2-ylphenyl)diazene Chemical compound CC(C)C1=CC=CC=C1N=NC1=CC=CC=C1C(C)C MMNIKCLHZKAPGA-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- BVEIKFLZWBDLJG-UHFFFAOYSA-N 1-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC BVEIKFLZWBDLJG-UHFFFAOYSA-N 0.000 description 1
- COVKSLBAQCJQMS-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenoxy)methoxy]benzene Chemical compound C1=CC(Cl)=CC=C1OCOC1=CC=C(Cl)C=C1 COVKSLBAQCJQMS-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- HHOSMYBYIHNXNO-UHFFFAOYSA-N 2,2,5-trimethylhexane Chemical compound CC(C)CCC(C)(C)C HHOSMYBYIHNXNO-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OKVWYBALHQFVFP-UHFFFAOYSA-N 2,3,3-trimethylpentane Chemical compound CCC(C)(C)C(C)C OKVWYBALHQFVFP-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- LWZNQGJGMBRAII-UHFFFAOYSA-N 2-methylhexyl prop-2-enoate Chemical compound CCCCC(C)COC(=O)C=C LWZNQGJGMBRAII-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- AHWAAQOJHMFNIV-UHFFFAOYSA-N 2-tert-butylperoxy-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C AHWAAQOJHMFNIV-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 102100037815 Fas apoptotic inhibitory molecule 3 Human genes 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 101000878510 Homo sapiens Fas apoptotic inhibitory molecule 3 Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HTMMMSIQFWMMIJ-UHFFFAOYSA-N [3-[2,2-dimethyl-3-(6-prop-2-enoyloxyhexanoyloxy)propanoyl]oxy-2,2-dimethylpropyl] 6-prop-2-enoyloxyhexanoate Chemical compound C=CC(=O)OCCCCCC(=O)OCC(C)(C)COC(=O)C(C)(C)COC(=O)CCCCCOC(=O)C=C HTMMMSIQFWMMIJ-UHFFFAOYSA-N 0.000 description 1
- NKIDFMYWMSBSRA-UHFFFAOYSA-N [4-(2-methylprop-2-enoyloxymethyl)cyclohexyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CCC(COC(=O)C(C)=C)CC1 NKIDFMYWMSBSRA-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- HXTBYXIZCDULQI-UHFFFAOYSA-N bis[4-(methylamino)phenyl]methanone Chemical compound C1=CC(NC)=CC=C1C(=O)C1=CC=C(NC)C=C1 HXTBYXIZCDULQI-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
저색분산, 고광선투과율 등의 뛰어난 광학특성을 가지며, 광학 렌즈·프리즘재료에 요구되는 각종 특성 밸런스가 뛰어나고, 습열 조건과 같은 험한 실사용 조건에서도 굴절률의 분기를 발생시키지 않는 공중합체와 그것을 포함하는 경화성 수지 조성물을 제공한다.
지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b), 2관능 (메타)아크릴산에스테르(c)와, 2,4-디페닐-4-메틸-1-펜텐(d)을 포함하는 성분을 공중합하여 얻어지는 공중합체로서, 측쇄에 (c)유래의 반응성의 (메타)아크릴레이트기를 가지며, 말단에 (d)유래의 구조단위를 가지는 가용성 다관능 (메타)아크릴산에스테르 공중합체, 및 그것을 포함하는 경화성 수지 조성물이다. A copolymer having excellent optical properties such as low color dispersion and high light transmittance, excellent balance of properties required for an optical lens and prism material, and a copolymer which does not generate refractive index divergence even in harsh practical conditions such as wet heat conditions and a curability including the same It provides a resin composition.
Monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, bifunctional (meth) acrylic acid ester (c), and 2, 4- diphenyl- A copolymer obtained by copolymerizing a component containing 4-methyl-1-pentene (d), having a reactive (meth) acrylate group derived from (c) in the side chain and a structural unit derived from (d) in the terminal It is a soluble polyfunctional (meth) acrylic acid ester copolymer, and curable resin composition containing it.
Description
본 발명은 저(低)색분산, 고(高)광선투과율과 같은 뛰어난 광학특성, 내열성 및 가공성을 가지며, 아울러 습열 조건과 같은 험한 실사용 조건하에서의 광학특성, 저흡수성(低吸水性)과 무기재료와의 밀착성이 개선된 지환식 구조 및 알코올성 수산기를 가지는 가용성 다관능 (메타)아크릴산에스테르 공중합체와 그 제조방법, 및 그것을 사용한 경화성 수지 조성물 및 경화물에 관한 것이다. The present invention has excellent optical properties such as low color dispersion and high light transmittance, heat resistance and processability, and also has optical properties, low absorption and inorganic properties under harsh practical conditions such as wet heat conditions. The present invention relates to a soluble polyfunctional (meth) acrylic acid ester copolymer having an alicyclic structure and an alcoholic hydroxyl group with improved adhesion to materials, a method for producing the same, and a curable resin composition and a cured product using the same.
반응 활성이 있는 불포화 결합을 가지는 단량체의 대부분은 불포화 결합이 개열(開裂)하여, 연쇄 반응을 일으키는 촉매와 적절한 반응 조건을 선택함으로써 다량체를 생성할 수 있다. 일반적으로 불포화 결합을 가지는 단량체의 종류는 매우 다양하므로, 얻어지는 수지의 종류의 풍부함도 현저하다. 그러나 일반적으로 고분자 화합물이라고 칭하는 분자량 10,000 이상의 고분자량체를 얻을 수 있는 단량체의 종류는 비교적 적다. 예를 들면 에틸렌, 치환 에틸렌, 프로필렌, 치환 프로필렌, 스티렌, 알킬스티렌, 알콕시스티렌, 노보넨(norbornene), 각종 아크릴에스테르, 부타디엔, 시클로펜타디엔, 디시클로펜타디엔, 이소프렌, 말레산무수물, 말레이미드, 푸말산에스테르, 알릴 화합물 등을 대표적인 단량체로서 들 수 있다. 이들 단량체를 단독으로 또는 이들을 공중합시킴으로써 다종다양한 수지가 합성되고 있다. Most of the monomers having an unsaturated bond with reactive activity are capable of producing a multimer by selecting an appropriate reaction condition and a catalyst causing the unsaturated bond to cleave, resulting in a chain reaction. Generally, since the kind of monomer which has an unsaturated bond varies widely, the richness of the kind of resin obtained is also remarkable. However, there are relatively few kinds of monomers capable of obtaining a high molecular weight of 10,000 or more, generally referred to as a high molecular compound. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkyl styrene, alkoxy styrene, norbornene, various acrylic esters, butadiene, cyclopentadiene, dicyclopentadiene, isoprene, maleic anhydride, maleimide , Fumaric acid ester, allyl compound, etc. are mentioned as a typical monomer. Various resins are synthesize | combined by these monomers being independent or copolymerizing them.
이들 수지의 용도는 주로 비교적 저렴한 민생기기분야에 한정되어 있어, 광·전자재료분야에 있어서 고도의 내열성, 치수 안정성이나 미세 가공성이 요구되는 첨단기술분야에의 적용은 거의 없다. 그 이유로서는 통상 상기의 모노머로부터 합성되는 폴리머는 열가소성이며, 또한 역학적 특성을 만족시키기 위해 상당한 고분자량체로 할 필요가 있기 때문에, 내열성이나 미세 가공성과 같은 첨단기술분야에서 요구되는 특성이 희생되고 있다는 점을 들 수 있다. The use of these resins is mainly limited to the field of relatively inexpensive domestic devices, and there are few applications in the high-tech field where high heat resistance, dimensional stability and fine workability are required in the field of optoelectronic materials. The reason is that the polymer synthesized from the above-mentioned monomers is usually thermoplastic, and in order to satisfy the mechanical properties, it is necessary to make a substantial high molecular weight, so that the characteristics required in the high-tech fields such as heat resistance and fine workability are sacrificed. Can be mentioned.
이러한 비닐계의 열가소성 폴리머의 결점을 해결하는 방법으로서, 특허문헌 1∼3에는 (메타)아크릴로일기 또는 비닐에테르기를 펜던트(pendant)에 가지는 중합체가 개시되어 있다. 예를 들면 특허문헌 1에는 아크릴산 2-비닐옥시에틸(VEA) 등의 이종(異種) 중합성 단량체를 양이온 중합시켜서 얻어진 (메타)아크릴로일기 펜던트형 중합체 및 광중합 개시제로 이루어지는 감광성 조성물이 개시되어 있다. 또한 특허문헌 2에는 (메타)아크릴로일기 펜던트형 중합체와, 광반응성의 불포화 카르복실기를 가지는 화합물과, 광중합 개시제로 이루어지는 감광성 조성물이 개시되어 있다. 또한 특허문헌 3에는 아크릴산 2-비닐옥시에틸(VEA) 등의 이종 중합성 단량체를, 그 자체 양이온 중합에 불활성인 광반응성의 불포화기를 가지는 카르복실산에스테르 용매 화합물 중에서, 양이온 중합 촉매를 사용해서 단독 중합 또는 공중합시킴으로써 중합체 용액을 얻는 제조법이 개시되어 있다. As a method of solving the drawback of such a vinyl-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth) acryloyl group or a vinyl ether group in a pendant. For example, Patent Document 1 discloses a photosensitive composition comprising a (meth) acryloyl group pendant polymer obtained by cationic polymerization of heteropolymerizable monomers such as 2-vinyloxyethyl acrylate (VEA) and a photopolymerization initiator. . In addition, Patent Document 2 discloses a photosensitive composition composed of a (meth) acryloyl group pendant polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. In addition, Patent Document 3 discloses a heteropolymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) alone using a cationic polymerization catalyst in a carboxylic ester solvent compound having a photoreactive unsaturated group which is inert to its own cationic polymerization. A method for producing a polymer solution by polymerizing or copolymerizing is disclosed.
그러나 이들 특허문헌에서 개시되어 있는 이종 중합성 단량체를 사용한 기술에 따라 제조되는 반응성의 중합체를 사용했을 경우, 선진 광학 렌즈·프리즘 용도분야에서 요구되는 저흡수성, 성형성, 내열성, 고투명성과 같은 특성 밸런스를 겸비하고, 아울러 습열 조건과 같은 험한 실사용 조건하에서의 광학특성과, 무기재료와의 밀착성이 개선된 중합체는 얻어지지 않고 있었다. However, in the case of using a reactive polymer prepared according to a technique using a heteropolymerizable monomer disclosed in these patent documents, properties such as low water absorption, moldability, heat resistance and high transparency required in the field of advanced optical lens prism applications are required. In addition, polymers having improved optical properties and adhesion to inorganic materials under harsh practical conditions such as wet heat conditions have not been obtained.
한편 특허문헌 4에는 모노비닐 방향족 화합물 및 2관능 (메타)아크릴산에스테르를 공중합해서 얻어지고, 측쇄에 2관능 (메타)아크릴산에스테르 유래의 반응성의 (메타)아크릴레이트기를 함유하는 구조단위를 가지는 가용성 다관능 비닐 방향족 공중합체가 개시되어 있다. 그러나 당해 특허문헌에서 개시되어 있는 기술에 의해 얻어지는 가용성 다관능 비닐 방향족 공중합체는 고온에서의 열이력에 대해서도 뛰어난 내열분해성을 가지고, 측쇄에 반응성의 (메타)아크릴레이트기를 가지며, 가공성이 뛰어나고, 용제 가용성을 겸비하고 있긴 하지만, 저색분산 용도의 광학 렌즈에는 사용할 수는 없다는 실사용상의 제약이 있는데다가, 무기재료와의 밀착성이 개선되지 않은 재료였다. On the other hand, Patent Document 4 is a soluble copolymer having a structural unit obtained by copolymerizing a monovinyl aromatic compound and a bifunctional (meth) acrylic acid ester and containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester in a side chain. Functional vinyl aromatic copolymers are disclosed. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in this patent document has excellent thermal decomposition resistance against thermal history at high temperature, has a reactive (meth) acrylate group in the side chain, and is excellent in workability and solvent. Although it has solubility, there is a practical use restriction that it cannot be used for an optical lens for low color dispersion, and the material has not improved the adhesion with the inorganic material.
또한 특허문헌 5에는 메타크릴산메틸(MMA)계 시럽에 있어서, 구성 성분으로서 탄소수 4∼8의 직쇄상 지방족 2가 알코올의 디(메타)아크릴레이트를 1∼25중량%함유하는 것을 특징으로 하는 조성물이 개시되어 있다. 그리고 당해 특허문헌에 개시되어 있는 MMA계 시럽 조성물의 제조는 MMA 혹은 MMA 및 그것과 공중합할 수 있는 비닐 공중합체, 연쇄이동제를 중합개시제의 존재하에서, 불활성 가스(예를 들면 N2 가스) 분위기 중, 상온 또는 가열 중합하여 실시하는 것이 개시되어 있다. 그리고 당해 공개특허공보에서 연쇄이동제로서 구체적으로 예시되어 있는 것은 라우릴메르캅탄, 티오글리콜산옥틸에스테르, 티오크레졸, 티오나프톨, 벤질메르캅탄 등의 유황 화합물뿐이며, 2,4-디페닐-4-메틸-1-펜텐(d)에 대해서는 구체적으로는 개시되어 있지 않았다. 더욱이 2,4-디페닐-4-메틸-1-펜텐 유래의 말단기와 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a) 유래의 구조단위가 공존함으로써, 상승적으로 습열시의 굴절률 분기의 발생을 억제할 수 있다는 것은 시사조차 되어 있지 않았다. 게다가 당해 특허문헌에서 개시되어 있는 기술에 의해 얻어지는 조성물은 습열 조건과 같은 험한 실사용 조건하에서의 무기재료와의 밀착성이 개선된 것은 아니었다. Further, Patent Document 5 contains 1 to 25% by weight of di (meth) acrylate of a linear aliphatic dihydric alcohol having 4 to 8 carbon atoms as a constituent in methyl methacrylate (MMA) syrup. A composition is disclosed. In the preparation of the MMA syrup composition disclosed in the patent document, MMA or MMA and a vinyl copolymer and a chain transfer agent copolymerizable with the same may be prepared in an inert gas (for example, N 2 gas) atmosphere in the presence of a polymerization initiator. It is disclosed to carry out at room temperature or by heat polymerization. Specific examples of the chain transfer agent in the publication include only sulfur compounds such as lauryl mercaptan, thioglycolic acid octyl ester, thiocresol, thionaphthol and benzyl mercaptan, and 2,4-diphenyl-4-. It does not disclose specifically about methyl-1- pentene (d). Furthermore, since the structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has a terminal group derived from 2, 4- diphenyl-4-methyl-1- pentene, and an alicyclic structure coexists, the refractive index branching at the time of wet heat is synergistically. It is not even suggested that the occurrence of can be suppressed. Moreover, the composition obtained by the technique disclosed by the said patent document did not improve adhesiveness with an inorganic material under harsh actual conditions, such as wet heat conditions.
또한 특허문헌 6에는 비닐계 단량체와 디(메타)아크릴레이트 화합물로 이루어지는 중합성 조성물이 개시되어 있으며, 2,4-디페닐-4-메틸-1-펜텐(d)의 사용도 개시되어 있긴 하지만, 그 사용량은 통상의 연쇄이동제로서 콤마 수% 정도의 사용이며, 생성물도 가교 겔화한 것으로 용제 가용성을 나타내지 않는 것이었다. In addition, Patent Document 6 discloses a polymerizable composition comprising a vinyl monomer and a di (meth) acrylate compound, and although the use of 2,4-diphenyl-4-methyl-1-pentene (d) is also disclosed. The amount of use was about comma about several percent as a conventional chain transfer agent, and the product was also crosslinked and gelled and did not show solvent solubility.
또한 특허문헌 7에는 1)에폭시기함유 (메타)아크릴레이트, 2)수산기함유 (메타)아크릴레이트, 3)(메타)아크릴산, 4)방향족기함유 (메타)아크릴레이트로 이루어지는 구성단위를 포함하는 자기경화성 공중합체와 유기 용매를 포함하는 컬러 필터용 열경화성 수지 조성물이 개시되어 있다. 그리고 당해 특허문헌에서 개시되어 있는 기술에 의해 얻어지는 자기경화성 공중합체는 중합 단계에 있어서, 바람직한 분자량의 범위를 달성하기 위해 메르캅토프로피온산, 메르캅토프로피온산에스테르, 티오글리콜, 티오글리세린, 도데실메르캅탄, α-메틸스티렌 다이머 등의 공지의 분자량 조절제를 사용할 수 있는 것이 개시되어 있다. 그러나 당해 특허문헌에서 개시된 기술에서는 중합시에 비닐기를 복수개 가지는 2관능 이상의 비닐 화합물이 첨가되어 있지 않기 때문에, 폴리머쇄에 1개 이하의 분자량 조절제 유래의 말단기밖에 도입할 수 없어, 말단기 유래의 기능 부여를 충분히 할 수 없다는 결점이 있었다. 또한 당해 특허공보에 있어서, 개시되어 있는 기술에 의해 얻어지는 자기경화성 공중합체는 에폭시 수지와의 수지 조성물에 있어서, 열경화성 수지 조성물을 형성하기는 하지만, 아크릴레이트 수지와의 사이에는 경화 반응이 일어나지 않기 때문에, 배합한 수지 조성물의 강도, 내열성의 저하를 일으킨다는 결점도 있었다. In addition, Patent Literature 7 discloses a porcelain comprising a structural unit comprising 1) an epoxy group-containing (meth) acrylate, 2) a hydroxyl group-containing (meth) acrylate, 3) (meth) acrylic acid, and 4) aromatic group-containing (meth) acrylate. A thermosetting resin composition for color filters comprising a curable copolymer and an organic solvent is disclosed. And the self-curable copolymer obtained by the technique disclosed in this patent document is a mercaptopropionic acid, mercaptopropionic acid ester, thioglycol, thioglycerine, dodecyl mercaptan, It is disclosed that known molecular weight regulators such as α-methylstyrene dimer can be used. However, in the technique disclosed in this patent document, since at least one bifunctional or higher vinyl compound having a plurality of vinyl groups is not added at the time of polymerization, only one or more terminal groups derived from one or less molecular weight regulators can be introduced into the polymer chains, and thus the terminal groups are derived from terminal groups. The drawback was that it could not be fully functionalized. Moreover, in the said patent publication, although the self-curable copolymer obtained by the technique disclosed forms a thermosetting resin composition in the resin composition with an epoxy resin, since hardening reaction does not arise between an acrylate resin, There also existed a fault that the intensity | strength and heat resistance fall of the resin composition mix | blended are caused.
따라서 저색분산, 고광선투과율과 같은 뛰어난 광학특성을 가지며, 저흡수성, 성형성, 내열성과 같은 특성 밸런스를 구비하고, 아울러 습열 조건과 같은 험한 실사용 조건하에서의 광학특성과 무기재료와의 밀착성이 개선된 가용성 다관능 (메타)아크릴산에스테르 공중합체는 지금까지 존재하지 않았다. Therefore, it has excellent optical characteristics such as low color dispersion and high light transmittance, balances characteristics such as low absorption, moldability, and heat resistance, and improves the optical properties and the adhesion between the inorganic materials under harsh practical conditions such as wet heat conditions. Soluble polyfunctional (meth) acrylic acid ester copolymers have not existed to date.
한편 열경화성의 수지 조성물은 예를 들면 기계부품재료, 전기·전자부품재료, 자동차부품재료, 토목건축재료, 성형재료 등으로서 유용하며, 또한 도료나 접착제의 재료로서도 이용되는 것이다. 나아가 무기 기재(基材)와 조합시켜 하이브리드 부재로 하면, 열팽창률을 저하시킬 수 있을 뿐 아니라 무기 물질과 수지와의 굴절률을 맞춤으로써 수지 조성물 및 그 경화물의 외관을 제어하여 투명성을 발현시킬 수도 있으므로, 전기·전자부품재료나 광학 용도에 있어서의 재료로서 특히 유용하다. 예를 들면 디지털 카메라 모듈은 휴대전화에 탑재되는 등 소형화가 진행되고, 저비용화도 요구되고 있다. 나아가 신규 용도로서 차재용(車載用) 카메라나 택배 업자용 바코드 판독기 등의 니즈가 높아지고 있다. 이들 용도에 적용할 때, 제조시의 솔더 리플로우시에 성형품 형상이 변화되지 않도록 형상유지의 내열성이 요구되고 있을 뿐 아니라, 실사용시에 있어서 여름철의 고온 노출 등을 고려하여 장시간의 내열성, 저흡수성 등의 높은 신뢰성이 요구되고 있다. On the other hand, a thermosetting resin composition is useful as a machine part material, an electric / electronic part material, an automobile part material, a civil engineering building material, a molding material, etc., and is used also as a material of a coating material and an adhesive agent. Furthermore, when combined with an inorganic substrate to form a hybrid member, not only can the thermal expansion coefficient be lowered, but also the refractive index of the inorganic substance and the resin can be adjusted to control the appearance of the resin composition and the cured product so that transparency can be expressed. It is especially useful as a material in electrical and electronic component materials and optical use. For example, the digital camera module is being miniaturized, such as being mounted in a mobile phone, and the cost is also required. Further, as new applications, there is an increasing need for in-vehicle cameras and bar code readers for parcel delivery companies. When applied to these applications, not only the heat resistance of the shape maintenance is required so that the shape of the molded product does not change during the solder reflow during manufacture, but also the long-term heat resistance and low water absorption in consideration of high temperature exposure in summer during use. Such high reliability is required.
이러한 기술요구에 대하여, 특허문헌 8에는 (a)유기 용제에 분산된 콜로이달 실리카, (b)지환식 폴리에폭시 화합물 및 (c)금속 킬레이트 화합물을 필수 성분으로서 함유하면서, (a)성분과 (b)성분의 배합비율이 고형분비로 (a)성분 5∼85중량% 및 (b)성분 95∼15중량%이고, 그리고 (c)성분이 (a)성분 및 (b)성분의 고형분의 합계 100중량부당 0.01∼30중량부 함유되는 유기 용제계 열경화성 조성물이 개시되어 있다. 또한 특허문헌 9∼11에는 에폭시 수지 및 무기 산화물 입자를 적어도 포함해서 이루어지는 조성물을 경화시킴으로써 성형한 에폭시 수지 성형체로서, 상기 성형체 내에 평균 입경이 50nm 이하인 무기 산화물 입자가 분산되어 있는 에폭시 수지 성형체가 개시되어 있다. 이들 문헌에서 개시되어 있는 기술에 의해 얻어진 재료는 280℃ 이상의 온도의 리플로우시의 가혹한 열이력을 받았을 경우에는 내열변색이 부족해, 열이력을 받은 후의 광학특성을 향상시킬 필요가 있었다. Regarding such technical requirements, Patent Document 8 includes (a) a component and (a) a colloidal silica dispersed in an organic solvent, (b) an alicyclic polyepoxy compound, and (c) a metal chelate compound as essential components. b) The compounding ratio of component is solid content ratio of 5 to 85 weight% of (a) component and 95 to 15 weight% of (b) component, and (c) component is the sum total of solid content of (a) component and (b) component 100 An organic solvent-based thermosetting composition containing 0.01 to 30 parts by weight per weight part is disclosed. In addition, Patent Documents 9 to 11 disclose an epoxy resin molded body molded by curing a composition comprising at least an epoxy resin and inorganic oxide particles, wherein an epoxy resin molded body in which inorganic oxide particles having an average particle diameter of 50 nm or less is dispersed in the molded body. have. When the material obtained by the technique disclosed by these documents receives severe heat history at the time of reflow of 280 degreeC or more, heat discoloration lacks and it is necessary to improve the optical characteristic after receiving the heat history.
한편 특허문헌 12에는 2관능의 축합한 다환의 지환식 구조를 가지는 적어도 1종 이상의 (메타)아크릴레이트(a), 평균 입자경이 1∼100nm인 실리카 미립자(b)가 유기 용매에 분산된 콜로이달 실리카를 포함하는 조성물의 유기 용매를 제거하여 얻어지는 복합체 조성물에 있어서, 실리카 미립자(b)의 함유량이 30∼90중량%인 복합체 조성물을 가교시켜 이루어지는 성형 경화물이 개시되어 있다. 그러나 당해 문헌의 기술에 따라 얻어지는 성형 경화물은 광학 렌즈 또는 프리즘과 같은 고(高)정밀도의 형상인 것을 연속 성형하는데에 필요한 성형성을 가지는 것은 아니었다. On the other hand, Patent Document 12 discloses a colloidal in which at least one (meth) acrylate (a) having a bifunctional condensed polycyclic alicyclic structure and silica fine particles (b) having an average particle diameter of 1 to 100 nm are dispersed in an organic solvent. In a composite composition obtained by removing an organic solvent of a composition containing silica, a molded cured product obtained by crosslinking a composite composition having a content of silica fine particles (b) of 30 to 90% by weight is disclosed. However, the molded cured product obtained according to the technique of this document did not have the moldability necessary for continuous molding of a high precision shape such as an optical lens or a prism.
또한 특허문헌 13에는 특정 구조의 이종 중합성 단량체로부터 유도되는 반복 구조단위를 가지는 비닐계 중합체와, 평균 입자경이 1nm∼100nm인 산화지르코늄 입자를 함유하는 광학재료용 경화성 수지 조성물이 개시되어 있다. In addition, Patent Document 13 discloses a curable resin composition for an optical material containing a vinyl polymer having a repeating structural unit derived from a heteropolymerizable monomer having a specific structure and zirconium oxide particles having an average particle diameter of 1 nm to 100 nm.
여기서는 무기 미립자로서, 평균 입자경이 1nm∼100nm인 산화지르코늄 입자를 사용하고 있다. 이러한 재료를 촬상계의 광학 렌즈로서 사용할 경우, 고분산의 재료가 되어버리기 때문에, 빛의 번짐을 작게 하고 높은 아베수(Abbe number)의 재료로 하기 위해 광학특성을 향상시킬 필요가 있었다. 또한 고온의 리플로우시의 가혹한 열이력을 받았을 경우에는 형상유지에 관한 내열성이 부족해, 열이력을 받은 후의 광학특성을 향상시킬 필요가 있었다. Here, zirconium oxide particles having an average particle diameter of 1 nm to 100 nm are used as the inorganic fine particles. When such a material is used as an optical lens of an imaging system, since it becomes a highly dispersed material, it is necessary to improve optical characteristics in order to make light blur and to make a material with a high Abbe number. In addition, in the case of receiving a severe thermal history during high temperature reflow, heat resistance related to shape retention was insufficient, and it was necessary to improve the optical characteristics after receiving the thermal history.
이들 문헌에서 개시되어 있는 기술에 따라 제조되는 경화성 복합체 조성물을 사용했을 경우, 선진 광학 렌즈·프리즘 용도분야에서 요구되는 저흡수성, 성형성, 내열성, 고투명성과 같은 특성 밸런스를 겸비하고, 아울러 고도의 내열성, 형상 정밀도, 내열 형상유지 안정성 등의 기본 성능을 구비한 것으로서, 높은 광학특성을 가지며, 각종 광학부재를 연속 성형하는데에 바람직하게 적용할 수 있는 경화성 수지 조성물은 얻어지지 않고 있었다. When the curable composite composition prepared according to the techniques disclosed in these documents is used, it has a balance of properties such as low water absorption, moldability, heat resistance and high transparency required in the field of advanced optical lens prism applications, and also has high heat resistance. And a curable resin composition having basic optical properties such as shape accuracy and heat-resistant shape retention stability, which have high optical characteristics and can be preferably applied to continuous molding of various optical members.
본 발명은 저색분산, 고광선투과율과 같은 뛰어난 광학특성을 가지고, 측쇄에 경화성이 뛰어난 반응성 (메타)아크릴레이트기를 가지며, 저흡수성, 가공성, 내열성과 같은 선진기술분야에 있어서 광학 렌즈·프리즘재료에 요구되는 각종 특성 밸런스가 뛰어나고, 아울러 습열 조건과 같은 험한 실사용 조건하에서의 광학특성과 무기재료와의 밀착성이 개선된 가용성 다관능 (메타)아크릴산에스테르 공중합체와 당해 공중합체를 고효율로 제조하는 제조방법을 제공하는 것을 목적으로 한다. 또한 본 발명은 저색분산, 고광선투과율과 같은 뛰어난 광학특성, 내열성, 경도 및 가공성을 가지며, 아울러 리플로우 조건과 같은 험한 실장 조건하에서의 성형품 형상의 내열유지성이 개선된 경화성 수지 조성물과 그 경화물을 제공하는 것을 목적으로 한다. The present invention has excellent optical properties such as low color dispersion and high light transmittance, has a reactive (meth) acrylate group excellent in curability in the side chain, and is required for an optical lens / prism material in advanced technical fields such as low absorption, workability and heat resistance. Soluble polyfunctional (meth) acrylic acid ester copolymer having excellent balance of characteristics and improved optical properties and adhesion between inorganic materials under harsh practical conditions such as wet heat conditions and a manufacturing method for producing the copolymer with high efficiency It aims to provide. The present invention also provides a curable resin composition having excellent optical properties such as low color dispersion and high light transmittance, heat resistance, hardness and processability, and improved heat resistance of a molded article shape under harsh mounting conditions such as reflow conditions and a cured product thereof. It aims to do it.
본 발명은 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b), 2관능 (메타)아크릴산에스테르(c)와, 2,4-디페닐-4-메틸-1-펜텐(d)을 포함하는 성분을 공중합하여 얻어지는 공중합체로서, 측쇄에 2관능 (메타)아크릴산에스테르(c) 유래의 반응성의 (메타)아크릴레이트기(c1)를 가지며, 말단에 2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위를 가지는 공중합체이고, 중량평균 분자량이 2000∼20000이며, 또한 톨루엔, 크실렌, 테트라하이드로푸란, 디클로로에탄 또는 클로로포름에 가용인 가용성 다관능 (메타)아크릴산에스테르 공중합체이다. The present invention is a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, a monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group, a bifunctional (meth) acrylic acid ester (c), and 2,4- As a copolymer obtained by copolymerizing the component containing diphenyl-4-methyl-1- pentene (d), it is a reactive (meth) acrylate group (c1) derived from bifunctional (meth) acrylic acid ester (c) in a side chain. Having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal, having a weight average molecular weight of 2000 to 20000, and further toluene, xylene, tetrahydrofuran, It is a soluble polyfunctional (meth) acrylic acid ester copolymer soluble in dichloroethane or chloroform.
본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체는 2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위의 도입량이 하기 식(1)로 표시되는 몰분율(Md)로서 0.02∼0.35인 것을 만족하는 것이 바람직하다. The soluble polyfunctional (meth) acrylic acid ester copolymer of the present invention has a molar fraction (M d ) in which the amount of the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) is represented by the following formula (1): ) Is preferably 0.02 to 0.35.
Md=(d)/[(a)+(b)+(c)+(d)] (1) M d = (d) / [(a) + (b) + (c) + (d)] (1)
또한 2관능 (메타)아크릴산에스테르(c) 유래의 반응성의 (메타)아크릴레이트기(c1)의 도입량이, 하기 식(2)로 표시되는 (c1)의 몰분율(Mc1)로서 0.05∼0.5인 것을 만족하는 것이 바람직하다. In addition, a 0.05 to 0.5 as a bifunctional (meth) mole fraction (M c1) of acrylic acid ester (c) (c1) represented by the introduced amount of the reactive (meth) acrylate group (c1), the following equation (2) derived from It is desirable to satisfy that.
Mc1=(c1)/[(a)+(b)+(c)] (2) M c1 = (c1) / [(a) + (b) + (c)] (2)
식 (1), (2)에 있어서 (a), (b), (c), (d) 및 (c1)은 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)에 유래하는 구조단위, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)에 유래하는 구조단위, 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위, 2,4-디페닐-4-메틸-1-펜텐(d)에 유래하는 구조단위, 및 측쇄에 2관능 (메타)아크릴레이트기를 함유하는 구조단위의 몰수를 나타낸다. In formulas (1) and (2), (a), (b), (c), (d) and (c1) are structural units derived from a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure. Structural unit derived from the monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, Structural unit derived from the bifunctional (meth) acrylic acid ester (c), 2, 4- diphenyl-4-methyl-1- The number of moles of the structural unit derived from pentene (d) and the structural unit containing a bifunctional (meth) acrylate group in a side chain are shown.
상기 단관능 (메타)아크릴산에스테르(a)가 이소보닐메타크릴레이트, 이소보닐아크릴레이트, 시클로헥실메타크릴레이트, 시클로헥실아크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 및 디시클로펜타닐메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 단관능 (메타)아크릴산에스테르이고, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)가 2-하이드록시프로필메타크릴레이트, 2-하이드록시에틸메타크릴레이트 및 부분적으로 에톡시화된 2-하이드록시메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 알코올성 수산기를 가지는 (메타)아크릴산에스테르이며, 2관능 (메타)아크릴산에스테르(c)가 시클로헥산디메탄올디아크릴레이트, 및 디메틸올트리시클로데칸디아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 2관능 (메타)아크릴산에스테르인 것을 만족하는 것이 바람직하다. The monofunctional (meth) acrylic acid ester (a) isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, At least one monofunctional (meth) acrylic acid ester selected from the group consisting of dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate In the group in which the monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group consists of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and partially ethoxylated 2-hydroxymethacrylate. It is (meth) acrylic acid ester which has 1 or more types of alcoholic hydroxyl groups selected, and bifunctional (meth) It is preferable to satisfy that acrylic acid ester (c) is 1 or more types of bifunctional (meth) acrylic acid ester chosen from the group which consists of cyclohexane dimethanol diacrylate and dimethylol tricyclodecane diacrylate.
또한 본 발명은 2,4-디페닐-4-메틸-1-펜텐(d)을 2관능 (메타)아크릴산에스테르(b) 100중량부에 대하여 10∼500중량부 존재시키고, 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)를 2∼55몰%, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)를 2∼50몰% 및 2관능 (메타)아크릴산에스테르(c)를 96∼10몰% 함유하여 이루어지는 단량체 성분을 50∼200℃의 온도로 중합시키는 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체의 제조방법이다. In addition, the present invention is 10 to 500 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (d) based on 100 parts by weight of the bifunctional (meth) acrylic acid ester (b), and has an alicyclic structure 2-50 mol% of monofunctional (meth) acrylic acid ester (a), 2-50 mol% of monofunctional (meth) acrylic acid ester (b) which has alcoholic hydroxyl group, and difunctional (meth) acrylic acid ester (c) 96 It is a manufacturing method of the soluble polyfunctional (meth) acrylic acid ester copolymer characterized by superposing | polymerizing at the temperature of 50-200 degreeC the monomer component containing -10 mol%.
또한 본 발명은 Also,
(A)성분: 청구항 1에 기재된 가용성 다관능 (메타)아크릴산에스테르 공중합체, (A) component: The soluble polyfunctional (meth) acrylic acid ester copolymer of Claim 1,
(B)성분: 불포화 이중결합을 가지는 관능기를 1개 이상 가지며, 분자량이 1000 이하인 모노머, 및 (B) component: Monomer which has one or more functional groups which have an unsaturated double bond, molecular weight is 1000 or less, and
(C)성분: 평균 입자경이 1∼100nm인 실리카 미립자, (C) component: the silica fine particle whose average particle diameter is 1-100 nm,
를 함유하는 것을 특징으로 하는 경화성 수지 조성물이다. It contains curable resin composition characterized by the above-mentioned.
상기 경화성 수지 조성물에 있어서의 (A)성분 및 (B)성분의 합계에 대한 (A)성분의 배합량이 2∼83wt%, (B)성분의 배합량이 83∼2wt%, (C)성분의 배합량이 15∼90wt%인 것이 좋다. 또한 상기 B 성분이 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르 및 2관능 (메타)아크릴산에스테르에서 선택되는 1종 이상의 (메타)아크릴산에스테르인 것이 좋다. 또한 상기 경화성 수지 조성물에는 (D)성분으로서 광중합 개시제를 포함할 수 있다. 또한 본 발명은 상기 경화성 수지 조성물을 경화시켜서 얻어지는 것을 특징으로 하는 경화물이다. The compounding quantity of (A) component with respect to the sum total of (A) component and (B) component in the said curable resin composition is 2 to 83 wt%, the compounding quantity of (B) component is 83 to 2 wt%, and the compounding quantity of (C) component It is good that it is 15-90 wt%. Moreover, it is good that said B component is 1 or more types of (meth) acrylic acid ester chosen from monofunctional (meth) acrylic acid ester and bifunctional (meth) acrylic acid ester which have an alicyclic structure. Moreover, a photoinitiator can be contained in the said curable resin composition as (D) component. Moreover, this invention is hardened | cured material obtained by hardening | curing the said curable resin composition.
본 발명에 의해, 저색분산, 고광선투과율과 같은 뛰어난 광학특성을 가지며, 측쇄에 광경화성이 뛰어난 반응성 (메타)아크릴레이트기를 가지며, 저흡수성, 가공성, 내열성과 같은 선진기술분야에 있어서 광학 렌즈·프리즘재료에 요구되는 각종 특성 밸런스가 뛰어나고, 아울러 습열 조건과 같은 험한 실사용 조건하에서의 광학특성과 무기재료와의 밀착성이 개선된 용제 가용성 다관능 (메타)아크릴산에스테르 공중합체를 고효율로 제조할 수 있다. 본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체를 경화시킴으로써 광학 렌즈·프리즘재료로서 뛰어난 수지가 된다. 또한 저색분산, 고광선투과율과 같은 뛰어난 광학특성, 내열성, 경도 및 가공성을 가지며, 아울러 리플로우 조건과 같은 험한 실장 조건하에서의 성형품 형상의 내열유지성이 개선된 경화성 수지 조성물과 그 경화물을 제공할 수 있다. INDUSTRIAL APPLICABILITY The present invention has excellent optical properties such as low color dispersion and high light transmittance, and has a reactive (meth) acrylate group having excellent photocurability in the side chain, and an optical lens prism in the advanced technical fields such as low absorption, workability and heat resistance. The solvent-soluble polyfunctional (meth) acrylic acid ester copolymer which is excellent in the balance of the various characteristics required for a material, and which improves the optical characteristic and adhesiveness with an inorganic material under the harsh actual conditions, such as wet heat conditions, can be manufactured at high efficiency. By hardening the soluble polyfunctional (meth) acrylic acid ester copolymer of this invention, it becomes resin excellent as an optical lens prism material. In addition, it is possible to provide a curable resin composition having excellent optical properties such as low color dispersion and high light transmittance, heat resistance, hardness and processability, and improved heat resistance of a molded article shape under harsh mounting conditions such as reflow conditions and a cured product thereof. .
이하, 본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체 및 그 제조방법에 대하여 상세하게 설명한다. 이 가용성 다관능 (메타)아크릴산에스테르 공중합체는 지환식 구조 및 수산기를 가진다. 이하, 이 가용성 다관능 (메타)아크릴산에스테르 공중합체를 공중합체라고 약칭하는 경우가 있다. Hereinafter, the soluble polyfunctional (meth) acrylic acid ester copolymer of this invention and its manufacturing method are demonstrated in detail. This soluble polyfunctional (meth) acrylic acid ester copolymer has an alicyclic structure and a hydroxyl group. Hereinafter, this soluble polyfunctional (meth) acrylic acid ester copolymer may be abbreviated as a copolymer.
본 발명의 공중합체는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b) 및 2관능 (메타)아크릴산에스테르(c)를 포함하는 단량체와, 2,4-디페닐-4-메틸-1-펜텐(d)을 존재시켜 공중합해서 얻어지는 공중합체로서, 측쇄에 2관능 (메타)아크릴산에스테르(c) 유래의 반응성의 (메타)아크릴레이트기를 가지며, 또한 말단에 2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위를 가지는 가용성 다관능 (메타)아크릴산에스테르 공중합체이다. 여기서 가용성이란 톨루엔, 크실렌, 테트라하이드로푸란, 디클로로에탄 또는 클로로포름에 가용인 것을 의미한다. 가용성 시험은 뒤에 기술하는 조건으로 이루어진다. The copolymer of the present invention comprises a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, a monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group, and a bifunctional (meth) acrylic acid ester (c) Reactive (meth) acryl derived from bifunctional (meth) acrylic acid ester (c) to a side chain as a copolymer obtained by copolymerizing a monomer and 2, 4- diphenyl-4-methyl-1- pentene (d) in presence. It is a soluble polyfunctional (meth) acrylic acid ester copolymer which has a rate group and has a structural unit derived from 2, 4- diphenyl-4-methyl-1- pentene (d) at the terminal. Soluble here means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The availability test is made under the conditions described below.
공중합체는 단관능 (메타)아크릴산에스테르 및 2관능 (메타)아크릴산에스테르를 공중합하여 얻어지는 것이므로 분기 구조 또는 가교 구조를 가지는데, 이러한 구조의 존재량은 가용성을 나타내는 정도로 제한된다. 따라서 2관능 (메타)아크릴산에스테르(c) 유래의 미반응의 (메타)아크릴기(c1)를 함유하는 구조단위를 측쇄에 가지는 공중합체로 되어 있다. 이 미반응의 (메타)아크릴기는 펜던트 (메타)아크릴기라고도 하며, 이것은 중합성을 나타내기 때문에 한층 더한 중합 처리에 의해 중합하여 용제 불용의 수지 경화물을 제공할 수 있다. Since a copolymer is obtained by copolymerizing a monofunctional (meth) acrylic acid ester and a bifunctional (meth) acrylic acid ester, it has a branched structure or a crosslinked structure, but the amount of such a structure is limited to the extent which shows solubility. Therefore, it becomes a copolymer which has in a side chain the structural unit containing the unreacted (meth) acryl group (c1) derived from bifunctional (meth) acrylic acid ester (c). This unreacted (meth) acryl group is also called a pendant (meth) acryl group, and since it shows polymerizability, it can superpose | polymerize by further polymerization process and can provide the resin hardened | cured material of a solvent insoluble.
또한 공중합체는 2,4-디페닐-4-메틸-1-펜텐(d)에 유래하는 구조단위를 말단에 가진다. 공중합체의 말단에 이 구조단위를 도입함으로써 이형성(離型性) 등의 성형 가공성이 향상된 경화물이 얻어지게 된다. In addition, the copolymer has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal. By introducing this structural unit at the terminal of the copolymer, a cured product having improved moldability such as mold release property can be obtained.
공중합체는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)에 유래하는 구조단위, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)에 유래하는 단위, 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위, 및 2,4-디페닐-4-메틸-1-펜텐(d)에 유래하는 구조단위를 가진다. 여기서 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위에는 2개의 (메타)아크릴산에스테르기에 포함되는 중합성 이중결합(비닐기라고 함) 양방이, 중합에 관여하여 분기 구조 또는 가교 구조를 형성하는 구조단위(c2)와, 1개의 비닐기만 중합에 관여하고 다른 비닐기는 반응하지 않고 남는 미반응의 (메타)아크릴기를 함유하는 구조단위(c1)가 있다. 2,4-디페닐-4-메틸-1-펜텐(d)은 연쇄이동제로서 작용하여 분자량의 증대를 방지하며 공중합체의 말단에 존재한다. The copolymer is a structural unit derived from a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, a unit derived from a monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group, and a bifunctional (meth) acrylic acid ester The structural unit derived from (c) and the structural unit derived from 2, 4- diphenyl-4-methyl-1- pentene (d) are included. In the structural unit derived from the bifunctional (meth) acrylic acid ester (c), both polymerizable double bonds (called vinyl groups) contained in two (meth) acrylic acid ester groups are involved in the polymerization to form a branched structure or a crosslinked structure. There is a structural unit (c1) containing a structural unit (c2) to be formed, and an unreacted (meth) acrylic group which remains in one polymerization group, and the other vinyl group does not react. 2,4-Diphenyl-4-methyl-1-pentene (d) acts as a chain transfer agent to prevent an increase in molecular weight and is present at the end of the copolymer.
공중합체에의 2,4-디페닐-4-메틸-1-펜텐(d)의 도입량으로서는, 상기 식(1)로 표시되는 몰분율(Md)로서 0.02∼0.35, 바람직하게는 0.03∼0.30, 특히 바람직하게는 0.05∼0.15이다. As the amount of 2,4-diphenyl-4-methyl-1-pentene (d) introduced into the copolymer, the molar fraction (M d ) represented by the formula (1) is 0.02 to 0.35, preferably 0.03 to 0.30, Especially preferably, it is 0.05-0.15.
여기서 (a), (b), (c) 및 (d)는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)에 유래하는 구조단위, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)에 유래하는 단위, 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위, 및 2,4-디페닐-4-메틸-1-펜텐(d)에 유래하는 구조단위의 몰수(또는 몰분율)를 나타낸다. 공중합체의 말단에 2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위를 상기 범위에 도입함으로써 이형성 및 저흡수성을 향상시킬 수 있다. Here (a), (b), (c) and (d) are a monofunctional (meth) acrylic acid ester which has a structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and an alcoholic hydroxyl group ( The number of moles of the unit derived from b), the structural unit derived from the bifunctional (meth) acrylic acid ester (c), and the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) (or Mole fraction). Releasability and low water absorption can be improved by introducing a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) into the terminal at the end of the copolymer.
2관능 (메타)아크릴산에스테르(c)는 공중합체를 분기 또는 가교시킴과 동시에 펜던트 비닐기를 생성시켜 이 공중합체에 경화성을 부여하여, 경화시에 내열성을 발현시키기 위한 가교 성분으로서 중요한 역할을 수행한다. The bifunctional (meth) acrylic acid ester (c) branches or crosslinks the copolymer and simultaneously forms a pendant vinyl group to impart curability to the copolymer, thereby playing an important role as a crosslinking component for expressing heat resistance upon curing. .
2관능 (메타)아크릴산에스테르로서는 시클로헥산디메탄올디아크릴레이트, 디메틸올트리시클로데칸디아크릴레이트, 시클로헥산디메탄올디메타크릴레이트, 디메틸올트리시클로데칸디메타크릴레이트, 에틸렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 1,4-부탄디올디아크릴레이트, 헥산디올디아크릴레이트, 디에틸렌글리콜디아크릴레이트, 에틸렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 1,4-부탄디올디메타크릴레이트, 헥산디올디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트 등의 2관능 (메타)아크릴산에스테르를 이용할 수 있지만, 이들에 제한되는 것은 아니다. As bifunctional (meth) acrylic acid ester, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate, ethylene glycol diacrylate, Propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, Although bifunctional (meth) acrylic acid ester, such as hexanediol dimethacrylate and diethylene glycol dimethacrylate, can be used, it is not limited to these.
2관능 (메타)아크릴산에스테르의 바람직한 구체예로서는 비용, 중합 제어의 용이함 및 얻어진 폴리머의 내열성의 점에서 시클로헥산디메탄올디아크릴레이트, 또는 디메틸올트리시클로데칸디아크릴레이트가 바람직하게 이용된다. As a preferable specific example of bifunctional (meth) acrylic acid ester, cyclohexane dimethanol diacrylate or dimethylol tricyclodecane diacrylate is used preferably from a cost, the ease of superposition | polymerization control, and the heat resistance of the obtained polymer.
공중합체는 측쇄에 2관능 (메타)아크릴산에스테르(c) 유래의 반응성의 (메타)아크릴레이트기를 함유하는 구조단위(c1)를 가지는데, 상기 식(2)로 표시되는 구조단위(c1)의 몰분율(Mc1)이 0.05∼0.5인 것이 좋고, 바람직하게는 0.1∼0.3이다. The copolymer has a structural unit (c1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (c) in the side chain, and the structural unit (c1) represented by the formula (2) The mole fraction (M c1 ) is preferably 0.05 to 0.5, preferably 0.1 to 0.3.
여기서 식 중의 (c1)은 (메타)아크릴레이트기를 함유하는 구조단위(c1)의 몰수를 나타낸다. 상기 몰분율을 만족함으로써 광이나 열에서의 경화성이 풍부해, 경화 후의 내열성 및 기계적 특성이 뛰어난 성형품을 얻을 수 있다. Here, (c1) shows the number-of-moles of the structural unit (c1) containing a (meth) acrylate group. By satisfy | filling the said mole fraction, the molded article which is rich in sclerosis | hardenability in light and heat, and excellent in the heat resistance after hardening and mechanical characteristics can be obtained.
지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)는 공중합체의 용제 가용성, 저흡수성, 내열성, 광학특성 및 가공성을 개선하기 위해 중요하다. 이러한 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르로서는 이소보닐메타크릴레이트, 이소보닐아크릴레이트, 시클로헥실메타크릴레이트, 시클로헥실아크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜타닐메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르를 들 수 있지만, 이들에 제한되는 것은 아니다. 이들 성분으로부터 유도되는 구조단위가 지환식 구조를 가지는 공중합체 내에 도입됨으로 인해 중합체의 겔화를 막아 용매에의 용해성을 높일 수 있을 뿐 아니라, 공중합체의 저색분산성 등의 광학특성, 저흡수성, 내열성을 개선할 수 있다. Monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is important for improving solvent solubility, low water absorption, heat resistance, optical properties and processability of the copolymer. As monofunctional (meth) acrylic acid ester which has such an alicyclic structure, isobornyl methacrylate, isobonyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acryl Monofunctional having at least one alicyclic structure selected from the group consisting of latex, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Although (meth) acrylic acid ester is mentioned, It is not limited to these. Since the structural unit derived from these components is introduced into the copolymer having an alicyclic structure, it is possible to prevent the gelation of the polymer to improve the solubility in the solvent, as well as optical properties such as low color dispersion of the copolymer, low absorption and heat resistance. Can be improved.
바람직한 구체예로서는 비용, 겔화 방지 및 얻어진 폴리머의 성형 가공성의 점에서 이소보닐메타크릴레이트, 이소보닐아크릴레이트, 시클로헥실메타크릴레이트, 시클로헥실아크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜타닐메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르를 들 수 있다. Preferred embodiments include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate and dicyclopentenyl oxy in terms of cost, gelling prevention and molding processability of the obtained polymer. Having at least one alicyclic structure selected from the group consisting of ethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Monofunctional (meth) acrylic acid ester is mentioned.
알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)는 공중합체의 습열 조건과 같은 험한 실사용 조건하에서의 무기재료와의 밀착성을 개선하기 위해 중요하다. 이러한 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르로서는 2-하이드록시프로필메타크릴레이트, 2-하이드록시에틸메타크릴레이트 및 부분적으로 에톡시화된 2-하이드록시메타크릴레이트 등을 들 수 있지만, 바람직하게는 2-하이드록시에틸메타크릴레이트이다. 이들 알코올성 수산기를 가지는 (메타)아크릴산에스테르계 단량체는 단독으로 사용해도 되고 2종류 이상을 병용해도 된다. The monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group is important for improving the adhesion with the inorganic material under harsh practical use conditions such as wet heat conditions of the copolymer. Examples of the monofunctional (meth) acrylic acid ester having an alcoholic hydroxyl group include 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and partially ethoxylated 2-hydroxymethacrylate. Preferably 2-hydroxyethyl methacrylate. The (meth) acrylic acid ester monomer which has these alcoholic hydroxyl groups may be used independently, or may use two or more types together.
알코올성 수산기를 함유하는 단관능 (메타)아크릴산에스테르(b)는 공중합체 중의 (a)성분, (b)성분 및 (c)성분의 몰분율과 알코올성 수산기를 함유하는 단관능 (메타)아크릴산에스테르(c) 유래의 구조단위의 몰분율(Mb)로서, 식(3)으로 계산되는 Mb가 0.05 이상, 0.60 이하인 것이 좋고, 바람직하게는 0.1∼0.3이다. Monofunctional (meth) acrylic acid ester (b) containing an alcoholic hydroxyl group is a monofunctional (meth) acrylic acid ester (c) containing the mole fraction of (a) component, (b) component, and (c) component in an copolymer, and an alcoholic hydroxyl group (c). As the mole fraction (M b ) of the structural unit derived from the C), it is preferable that M b calculated by the formula (3) is 0.05 or more and 0.60 or less, preferably 0.1 to 0.3.
Mb=(b)/[(a)+(b)+(c)] (3) M b = (b) / [(a) + (b) + (c)] (3)
식 중의 (a), (b) 및 (c)는 식(1)과 같은 의미이다. (A), (b) and (c) in a formula are synonymous with Formula (1).
상기 몰분율을 만족함으로써 습열 조건과 같은 험한 실사용 조건하에서의 광학특성과, 무기재료와의 밀착성을 개선할 수 있는 밸런스가 양호한 공중합체를 얻을 수 있다. By satisfy | filling the said mole fraction, the copolymer with a favorable balance which can improve the optical characteristic and adhesiveness with an inorganic material under harsh actual conditions, such as wet heat conditions, can be obtained.
2,4-디페닐-4-메틸-1-펜텐(c)은 연쇄이동제로서 기능하며 공중합체의 분자량을 제어한다. 본 발명의 공중합체의 분자량은 중량평균 분자량(Mw)으로서 2000∼20000의 범위이고, 바람직하게는 3000∼10000의 범위이다. 비교적 저분자량의 공중합체를 사용함으로써 수지 조성물 또는 경화물의 성형성 및 이형성을 높인다. 2,4-Diphenyl-4-methyl-1-pentene (c) functions as a chain transfer agent and controls the molecular weight of the copolymer. The molecular weight of the copolymer of this invention is 2000-20000 as a weight average molecular weight (Mw), Preferably it is the range of 3000-10000. By using a relatively low molecular weight copolymer, the moldability and mold release property of a resin composition or hardened | cured material are improved.
또한 공중합체의 용제 가용성 및 가공성을 개선할 목적으로 (e)성분으로서, 지환식 구조 및 수산기를 가지지 않는 단관능의 (메타)아크릴산에스테르를 첨가하는 것이 가능하다. 이러한 (메타)아크릴산에스테르로서는 메틸메타크릴레이트, 에틸메타크릴레이트, 메틸아크릴레이트, 에틸아크릴레이트, n-부틸아크릴레이트, 2-메틸헥실아크릴레이트, 2-에틸헥실아크릴레이트, 옥틸아크릴레이트 등을 들 수 있지만, 바람직하게는 메틸메타크릴레이트, n-부틸아크릴레이트이다. 이들 (메타)아크릴산에스테르계 단량체는 단독으로 사용해도 되고 2종류 이상을 병용해도 되지만, 메틸메타크릴레이트, 메틸아크릴레이트, n-부틸아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 (메타)아크릴산에스테르인 것이 가장 바람직하다. Moreover, it is possible to add the monofunctional (meth) acrylic acid ester which does not have an alicyclic structure and a hydroxyl group as (e) component in order to improve the solvent solubility and processability of a copolymer. As such (meth) acrylic acid ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, etc. Although it is mentioned, Preferably they are methyl methacrylate and n-butyl acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of two or more, but at least one (meth) acrylic acid ester selected from the group consisting of methyl methacrylate, methyl acrylate and n-butyl acrylate Is most preferred.
또한 이들 기타 단량체 성분(e)에 유래하는 구조단위는 단량체 성분(a) 유래의 구조단위, 단량체 성분(b) 유래의 구조단위 및 단량체 성분(c) 유래의 구조단위의 총량에 대하여 30몰% 미만의 범위 내로 하는 것이 좋다. In addition, the structural unit derived from these other monomer components (e) is 30 mol% with respect to the total amount of the structural unit derived from the monomer component (a), the structural unit derived from the monomer component (b), and the structural unit derived from the monomer component (c). It is good to carry out within the range below.
본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b), 2관능 (메타)아크릴산에스테르(c)와, 2,4-디페닐-4-메틸-1-펜텐(d)을 포함하는 성분을 공중합하여 얻어지는 공중합체이므로 각각에 유래하는 구조단위를 가진다. 전체 구조단위를 100몰로 했을 경우, 각각에 유래하는 구조단위의 몰수를 (a), (b), (c) 및 (d)로 할 때 (a), (b)∼(d)는 다음 범위인 것이 좋다. (a)는 10∼55몰, (b)는 10∼45몰, (c)는 10∼50몰, 바람직하게는 15∼40몰, (d)는 2∼35몰, 바람직하게는 5∼20몰. The soluble polyfunctional (meth) acrylic acid ester copolymer of this invention is monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, bifunctional (meth) Since it is a copolymer obtained by copolymerizing the component containing acrylate ester (c) and 2, 4- diphenyl-4-methyl-1- pentene (d), it has a structural unit derived from each. When the total structural unit is 100 moles, when the moles of the structural units derived from each of them are (a), (b), (c) and (d), (a), (b) to (d) are in the following ranges It is good to be (a) is 10 to 55 mol, (b) is 10 to 45 mol, (c) is 10 to 50 mol, preferably 15 to 40 mol, (d) is 2 to 35 mol, preferably 5 to 20 mole.
또한 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위에는 반응성의 (메타)아크릴레이트기(c1)가 있는데, 이 (메타)아크릴레이트기를 포함하는 구조단위의 몰수(c1)는 전체 구조단위를 100몰로 했을 경우, 5∼35몰, 바람직하게는 10∼25몰로 하는 것이 좋다. 또한 (c1)은 (c)의 1/4∼3/4의 범위가 좋다. (c) 또는 (c1)이 너무 적으면 경화물의 내열성이 부족하고, 너무 많으면 성형 가공성이 저하하여, 성형물의 강도가 현저하게 저하한다. Moreover, although the structural unit derived from the bifunctional (meth) acrylic acid ester (c) has a reactive (meth) acrylate group (c1), the number-of-moles (c1) of the structural unit containing this (meth) acrylate group are the whole structure When the unit is 100 moles, it is preferably 5 to 35 moles, preferably 10 to 25 moles. In addition, (c1) may have a range of 1/4 to 3/4 of (c). If too little (c) or (c1), the heat resistance of hardened | cured material will run short, if too much, moldability will fall and the strength of a molded object will fall remarkably.
본 발명의 가용성 다관능 방향족 (메타)아크릴산에스테르 공중합체의 제조방법에서는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b), 2관능 (메타)아크릴산에스테르(c) 및 2,4-디페닐-4-메틸-1-펜텐(d)을 포함하는 단량체를 사용하고, 이들 단량체에 유래하는 구조단위의 몰수 또는 몰분율이 상기 범위가 되도록 사용량이 결정된다. 여기서 2,4-디페닐-4-메틸-1-펜텐(d)은 연쇄이동제로서도 공지의 화합물이지만, 본 발명에서는 그 사용량을 연쇄이동제로서의 사용량보다 다량으로 하므로 단량체 성분의 일부가 된다. 2,4-디페닐-4-메틸-1-펜텐(d)의 사용량은 본 발명의 가용성 다관능 방향족 (메타)아크릴산에스테르 공중합체 중에 포함되는 2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위의 몰분율이 0.02∼0.35의 범위가 되도록 조정되는데, 이것은 반응성이 낮아 미반응으로 남으므로 이론량보다 많이 사용하는 것이 좋다. 그 때문에 단량체 100몰에 대하여 2∼60몰의 범위로 사용되는데, 바람직하게는 10∼50몰의 범위이다. In the manufacturing method of the soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of this invention, the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and the monofunctional (meth) acrylic acid ester (b) which have an alcoholic hydroxyl group (b), 2 Using the monomer containing a functional (meth) acrylic acid ester (c) and 2,4-diphenyl-4-methyl-1-pentene (d), the number of moles or mole fraction of the structural unit derived from these monomers is The amount of usage is determined as possible. Here, 2,4-diphenyl-4-methyl-1-pentene (d) is a compound known as a chain transfer agent, but in the present invention, the amount of the 2,4-diphenyl-4-methyl-1-pentene (d) is greater than that used as the chain transfer agent, and thus becomes part of the monomer component. The amount of 2,4-diphenyl-4-methyl-1-pentene (d) used is 2,4-diphenyl-4-methyl-1- contained in the soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of the present invention. The mole fraction of the structural unit derived from pentene (d) is adjusted to be in the range of 0.02 to 0.35, which is low in reactivity and remains unreacted. Therefore, although it is used in the range of 2-60 mol with respect to 100 mol of monomers, Preferably it is the range of 10-50 mol.
본 발명의 가용성 다관능 방향족 (메타)아크릴산에스테르 공중합체의 제조방법에서는 2,4-디페닐-4-메틸-1-펜텐(d)을 2관능 (메타)아크릴산에스테르(c) 100중량부에 대하여 10∼500중량부 존재시키고, 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)를 2∼55몰%, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)를 2∼35몰% 및 2관능 (메타)아크릴산에스테르(c)를 96∼10몰% 함유하여 이루어지는 단량체 성분을 50∼200℃의 온도에서 중합시킨다. In the method for producing a soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of the present invention, 2,4-diphenyl-4-methyl-1-pentene (d) is added to 100 parts by weight of a bifunctional (meth) acrylic acid ester (c). 2-35 mol of monofunctional (meth) acrylic acid ester (a) which has 10-500 weight part with respect to an alicyclic structure, and has a monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group The monomer component which contains 96-10 mol% of% and a bifunctional (meth) acrylic acid ester (c) is polymerized at the temperature of 50-200 degreeC.
2,4-디페닐-4-메틸-1-펜텐(d)이 연쇄이동제로서도 기능한다는 관점에서는 이 사용량은 가교 반응의 제한, 펜던트 (메타)아크릴레이트기의 생성, 분자량 분포의 제어라고 하는 점에서 2관능 (메타)아크릴산에스테르(c) 100중량부에 대하여 10∼500중량부의 범위 내인 것이 바람직하고, 20∼100중량부의 범위 내인 것이 더욱 바람직하다. 50∼80중량부의 범위 내인 것이 가장 바람직하다. In view of the fact that 2,4-diphenyl-4-methyl-1-pentene (d) also functions as a chain transfer agent, this amount of use is limited to crosslinking reaction, formation of pendant (meth) acrylate groups, and control of molecular weight distribution. It is preferable to exist in the range of 10-500 weight part with respect to 100 weight part of bifunctional (meth) acrylic acid ester (c), and it is more preferable to exist in the range which is 20-100 weight part. It is most preferable to exist in the range of 50-80 weight part.
지환식 구조를 가지는 모노 (메타)아크릴산에스테르 방향족 화합물(a)의 사용량은 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a), 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b), 및 2관능 (메타)아크릴산에스테르(c)의 합계 100몰에 대하여 2∼55몰, 바람직하게는 10∼40몰이다. 2관능 (메타)아크릴산에스테르(c)의 사용량은 96∼10몰, 바람직하게는 20∼50몰%이다. 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)의 사용량은 2∼50몰%, 바람직하게는 10∼40몰%이다. The mono (meth) acrylic acid ester aromatic compound (a) which has an alicyclic structure has the usage-amount of monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, And it is 2-55 mol with respect to a total of 100 mol of bifunctional (meth) acrylic acid ester (c), Preferably it is 10-40 mol. The usage-amount of bifunctional (meth) acrylic acid ester (c) is 96-10 mol, Preferably it is 20-50 mol%. The usage-amount of the monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group is 2-50 mol%, Preferably it is 10-40 mol%.
본 발명의 제조방법에서는 열개시 반응에 의한 개시반응속도가 작을 경우에는 라디칼 중합개시제를 첨가할 수도 있다. 이 경우, 본 발명에서 사용되는 라디칼 중합개시제로서는 예를 들면 시클로헥사논퍼옥사이드, 3,3,5-트리메틸시클로헥사논퍼옥사이드, 메틸시클로헥사논퍼옥사이드 등의 케톤퍼옥사이드류; 1,1-비스(tert-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, 1,1-비스(tert-부틸퍼옥시)시클로헥산, n-부틸-4,4-비스(tert-부틸퍼옥시)발레레이트 등의 퍼옥시케탈류; 쿠멘하이드로퍼옥사이드, 2,5-디메틸헥산-2,5-디하이드로퍼옥사이드 등의 하이드로퍼옥사이드류; 1,3-비스(tert-부틸퍼옥시-m-이소프로필)벤젠, 2,5-디메틸-2,5-디(tert-부틸퍼옥시)헥산, 디이소프로필벤젠퍼옥사이드, tert-부틸쿠밀퍼옥사이드 등의 디알킬퍼옥사이드류; 데카노일퍼옥사이드, 라우로일퍼옥사이드, 벤조일퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드 등의 디아실퍼옥사이드류; 비스(tert-부틸시클로헥실)퍼옥시디카보네이트 등의 퍼옥시카보네이트류; tert-부틸퍼옥시벤조에이트, 2,5-디메틸-2,5-디(벤조일퍼옥시)헥산 등의 퍼옥시에스테르류 등의 유기 과산화물계 중합개시제 및 2,2'-아조비스이소부티로니트릴, 1,1-아조비스(시클로헥산-1-카르보니트릴), 아조쿠멘 2,2'-아조비스메틸발레로니트릴, 4,4'-아조비스(4-시아노길초산) 등의 아조계 중합개시제를 들 수 있다. 이들 라디칼 중합개시제의 사용량은 특별히 한정되는 것은 아니지만, 통상 단량체 성분의 합계량 100중량부에 기초하여 0.01∼25중량부인 것이 바람직하고, 0.05∼20중량부의 범위 내인 것이 더욱 바람직하다. 0.1∼15중량부의 범위 내인 것이 가장 바람직하다. In the production method of the present invention, when the initial reaction rate due to the thermal initiation reaction is small, a radical polymerization initiator may be added. In this case, examples of the radical polymerization initiator used in the present invention include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert- Peroxy ketals such as butyl peroxy) valerate; Hydroperoxides such as cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzeneperoxide, tert-butylco Dialkyl peroxides such as miper oxide; Diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; Peroxy carbonates such as bis (tert-butylcyclohexyl) peroxydicarbonate; organic peroxide-based polymerization initiators such as peroxy esters such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and 2,2'-azobisisobutyronitrile Azo systems such as 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2'-azobismethylvaleronitrile, and 4,4'-azobis (4-cyanogilacetic acid) And polymerization initiators. Although the usage-amount of these radical polymerization initiators is not specifically limited, Usually, it is preferable that it is 0.01-25 weight part based on 100 weight part of total amounts of a monomer component, and it is more preferable to exist in the range which is 0.05-20 weight part. It is most preferable to exist in the range of 0.1-15 weight part.
또한 중합 반응은 기본적으로 용제를 사용하지 않는 괴상(塊狀) 중합으로 실시할 수 있지만, 생성되는 가용성 다관능 (메타)아크릴산에스테르 방향족 공중합체를 용해하는 1종 이상의 유기 용매 중에서 실시할 수도 있다. 유기 용매로서는 라디칼 중합을 본질적으로 저해하지 않는 화합물로서, 본 발명의 연쇄이동제, 개시제, 단량체 및 다관능 (메타)아크릴산에스테르 방향족 공중합체를 용해하여 균일 용액을 형성하는 것이면 특별한 제약 없이 사용할 수 있다. Moreover, although a polymerization reaction can be basically performed by block polymerization which does not use a solvent, it can also carry out in 1 or more types of organic solvent which melt | dissolves the produced | generated soluble polyfunctional (meth) acrylic acid ester aromatic copolymer. As an organic solvent, it is a compound which does not essentially inhibit radical polymerization, and it can use without a restriction | limiting as long as it melt | dissolves the chain transfer agent, initiator, monomer, and polyfunctional (meth) acrylic acid ester aromatic copolymer of this invention, and forms a uniform solution.
유기 용매로서 사용 가능한 것으로서는 벤젠, 톨루엔, 크실렌, 에틸벤젠, 프로필벤젠, 부틸벤젠 등의 방향족 탄화수소; 에탄, 프로판, 부탄, 펜탄, 헥산, 헵탄, 옥탄, 노난, 데칸 등의 직쇄식 지방족 탄화수소류; 2-메틸프로판, 2-메틸부탄, 2,3,3-트리메틸펜탄, 2,2,5-트리메틸헥산 등의 분기식 지방족 탄화수소류; 시클로헥산, 메틸시클로헥산, 에틸시클로헥산 등의 환식 지방족 탄화수소류; 석유 증류분을 수첨(水添) 정제한 파라핀유 등을 들 수 있다. 이 중에서 톨루엔, 크실렌, 펜탄, 헥산, 헵탄, 옥탄, 2-메틸프로판, 2-메틸부탄, 시클로헥산, 메틸시클로헥산 및 에틸시클로헥산이 바람직하다. 중합성, 용해성의 밸런스와 입수 용이함의 관점에서 톨루엔, 크실렌, 메틸시클로헥산 및 에틸시클로헥산이 더욱 바람직하다. Examples of usable organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene; Linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane and decane; Branched aliphatic hydrocarbons such as 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane and 2,2,5-trimethylhexane; Cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; And paraffin oil obtained by hydrogenation of petroleum distillate. Among them, toluene, xylene, pentane, hexane, heptane, octane, 2-methylpropane, 2-methylbutane, cyclohexane, methylcyclohexane and ethylcyclohexane are preferable. Toluene, xylene, methylcyclohexane, and ethylcyclohexane are more preferable from the viewpoint of the balance of polymerizability, solubility and availability.
이들 유기 용매로서의 화합물은 단독 또는 2종 이상을 조합시켜서 사용된다. 용제의 사용량에 특별히 제한은 없다. The compound as these organic solvents is used individually or in combination of 2 or more types. There is no restriction | limiting in particular in the usage-amount of a solvent.
본 발명의 제조방법에서는 중합은 50∼200℃의 온도범위에서 실시한다. 50℃ 미만으로 중합 반응을 행하면 중합 속도가 낮아지므로 공업적 실시의 관점에서 바람직하지 않고, 또한 200℃를 넘으면 반응의 선택성이 저하하기 때문에 반응의 제어가 어려우며, 가교에 의한 불용성의 겔이 생성되기 쉬워지므로 바람직하지 않다. In the manufacturing method of this invention, superposition | polymerization is performed in the temperature range of 50-200 degreeC. When the polymerization reaction is carried out below 50 ° C., the polymerization rate is lowered, which is not preferable from the viewpoint of industrial practice. When the polymerization reaction is carried out below 200 ° C., the selectivity of the reaction is lowered. It is not preferable because it becomes easy.
중합 반응 정지 후 공중합체를 회수하는 방법은 특별히 한정되지 않으며, 예를 들면 가열 감압 탈휘법, 스팀 스트립핑(steam stripping)법, 빈(貧)용매로의 석출 등의 통상 이용되는 방법을 이용하면 된다. The method for recovering the copolymer after the termination of the polymerization reaction is not particularly limited. For example, if a commonly used method such as heating under reduced pressure devolatilization, steam stripping or precipitation into a poor solvent is used, do.
본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체, 또는 본 발명의 제조방법으로 얻어지는 가용성 다관능 (메타)아크릴산에스테르 공중합체는 성형재, 시트 또는 필름으로 가공할 수 있다. 이것을 가열 등에 의해 경화시킴으로써 경화물이 얻어진다. 가용성 다관능 (메타)아크릴산에스테르 공중합체, 그것을 성형재, 시트 또는 필름으로 가공한 성형품, 또는 이들을 경화시킨 경화 수지 또는 성형품은 저색분산, 저유전율, 저흡수율, 고내열성 등의 특성을 만족할 수 있는 광학용 재료 또는 반도체관련 재료, 나아가서는 도료, 감광성 재료, 접착제, 오수 처리제, 중금속 포집제, 이온교환 수지, 대전 방지제, 산화 방지제, 방담제(防曇劑), 방청제, 방염제, 의용재료, 응집제, 고체 연료용 바인더, 도전 처리제 등에의 적용이 가능하다. 또한 광학용 부품으로서는 CD용 픽업 렌즈, DVD용 픽업 렌즈, Fax용 렌즈, LBP용 렌즈, 폴리곤 미러(polygon mirror), 프리즘 등을 들 수 있다. The soluble polyfunctional (meth) acrylic acid ester copolymer of this invention or the soluble polyfunctional (meth) acrylic acid ester copolymer obtained by the manufacturing method of this invention can be processed into a molding material, a sheet, or a film. By hardening this by heating etc., hardened | cured material is obtained. A soluble polyfunctional (meth) acrylic acid ester copolymer, a molded article processed into a molding material, a sheet or a film, or a cured resin or molded article cured thereof may satisfy properties such as low color dispersion, low dielectric constant, low absorption rate, and high heat resistance. Optical materials or semiconductor-related materials, further paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal collecting agents, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rust inhibitors, flame retardants, medical materials, flocculants It is possible to apply to a solid fuel binder, a conductive treatment agent and the like. Examples of the optical component include a CD pickup lens, a DVD pickup lens, a fax lens, an LBP lens, a polygon mirror, a prism, and the like.
본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체는 톨루엔, 크실렌, THF, 디클로로에탄, 디클로로메탄 및 클로로포름에서 선택되는 용매 중 적어도 1개에 가용이다. 바람직하게는 상기 용매 전부에 가용이다. 여기서 가용이란, 실온(25℃)에서 100ml의 용매에 1g 이상, 바람직하게는 10g 이상이 용해되는 것을 말한다. 그리고 용해 후에 겔의 생성이 인정되지 않는 것이 바람직하다. The soluble polyfunctional (meth) acrylic acid ester copolymer of the present invention is soluble in at least one of solvents selected from toluene, xylene, THF, dichloroethane, dichloromethane and chloroform. Preferably it is soluble in all of the above solvents. Soluble means here that 1g or more, Preferably 10g or more melt | dissolves in 100 ml of solvent at room temperature (25 degreeC). And it is preferable that generation | occurrence | production of a gel after dissolution is not recognized.
다음으로 본 발명의 경화성 수지 조성물에 대하여 상세하게 설명한다. 본 발명의 경화성 수지 조성물은 (A)성분, (B)성분 및 (C)성분을 필수 성분으로서 포함하므로 필수 성분부터 설명한다. Next, the curable resin composition of this invention is demonstrated in detail. Since curable resin composition of this invention contains (A) component, (B) component, and (C) component as an essential component, it demonstrates from an essential component.
본 발명의 (A)성분인 가용성 다관능 (메타)아크릴산에스테르 공중합체(이하, 공중합체라고 약칭하기도 함)는 상기의 본 발명의 가용성 다관능 (메타)아크릴산에스테르 공중합체이다. The soluble polyfunctional (meth) acrylic acid ester copolymer (henceforth a copolymer hereafter) which is (A) component of this invention is the soluble polyfunctional (meth) acrylic acid ester copolymer of said this invention.
(B)성분으로서, 불포화 이중결합을 가지는 관능기를 1개 이상 가지는 (메타)아크릴레이트 모노머(이하, (메타)아크릴레이트 모노머라고 약칭하기도 함)가 사용된다. (메타)아크릴레이트 모노머는 분자 중에 1개 이상의 (메타)아크릴로일기를 가지는 것이며, 1종 또는 2종 이상이 사용된다. 이들 (B)성분으로서 사용되는 (메타)아크릴레이트는 (A)성분과 병용함으로써 경화성을 떨어뜨리지 않고 조성물의 점도를 조정하는 것이 가능하게 되는 동시에, 상승적으로, 내열성에 더하여 저색분산, 고광선투과율과 같은 광학특성이 동시에 향상된다. As (B) component, the (meth) acrylate monomer (henceforth abbreviated as a (meth) acrylate monomer) which has one or more functional groups which have an unsaturated double bond is used. The (meth) acrylate monomer has one or more (meth) acryloyl groups in the molecule, and one kind or two or more kinds are used. The (meth) acrylate used as these (B) components makes it possible to adjust the viscosity of a composition without degrading sclerosis | hardenability by using together with (A) component, and is synergistically low color dispersion, high light transmittance, and The same optical characteristic is improved at the same time.
(메타)아크릴레이트 모노머는 분자량이 1000 이하인 모노머인데, 폴리에틸렌글리콜디(메타)아크릴레이트와 같은 분자량 분포를 가지는 모노머일 수도 있으며, 이 경우의 Mw는 1000 이하이다. 유리하게는, 분자량 분포를 가지지 않는 화합물로 이루어지는 모노머 또는 그 혼합물이다. Although the (meth) acrylate monomer is a monomer whose molecular weight is 1000 or less, the monomer which has a molecular weight distribution like polyethyleneglycol di (meth) acrylate may be sufficient, and Mw in this case is 1000 or less. Advantageously, these are monomers or mixtures thereof composed of compounds having no molecular weight distribution.
상기 (메타)아크릴레이트 모노머로서는 (A)성분과 공중합 가능한 것이 좋고, 예를 들면 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)가 바람직하게 사용되지만, 그 밖에 예를 들어 아크릴로일모르폴린, 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트, 폴리에틸렌글리콜모노(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 시클로헥산-1,4-디메탄올모노(메타)아크릴레이트, 테트라하이드로푸르푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페닐폴리에톡시(메타)아크릴레이트, 2-하이드록시-3-페닐옥시프로필(메타)아크릴레이트, o-페닐페놀모노에톡시(메타)아크릴레이트, o-페닐페놀폴리에톡시(메타)아크릴레이트, p-쿠밀페녹시에틸(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 트리브로모페닐옥시에틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜테닐옥시에틸(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 1,9-노난디올디(메타)아크릴레이트, 트리시클로데칸디메탄올(메타)아크릴레이트, 비스페놀A폴리에톡시디(메타)아크릴레이트, 비스페놀A폴리프로폭시디(메타)아크릴레이트, 비스페놀F폴리에톡시디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 트리메틸올프로판트리옥시에틸(메타)아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 트리스(아크릴옥시에틸)이소시아누레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 트리펜타에리스리톨헥사(메타)아크릴레이트, 트리펜타에리스리톨펜타(메타)아크릴레이트, 하이드록시피발산네오펜글리콜디(메타)아크릴레이트, 하이드록시피발산네오펜글리콜의 ε-카프로락톤 부가물의 디(메타)아크릴레이트(예를 들면 닛폰카야쿠(주) 제품, KAYARAD HX-220, HX-620 등), 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판폴리에톡시트리(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트 등의 모노머류를 들 수 있다. 특히 바람직하게는 1,6-헥산디올디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판트리옥시에틸(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트를 들 수 있다. As said (meth) acrylate monomer, what is copolymerizable with (A) component is good, For example, the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure is used preferably, In addition, for example, acryloyl Morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Meta) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth )acryl Yit, isobonyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, tricyclodecanedimethanol (meth) acrylic Late, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane Trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Sa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta Ε- of (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxy pivalate neophenglycol di (meth) acrylate, hydroxy pivalate neophenglycol Di (meth) acrylate of caprolactone adduct (for example, Nippon Kayaku Co., KAYARAD HX-220, HX-620, etc.), trimethylol propane tri (meth) acrylate, trimethylol propane polyethoxy tree Monomers, such as (meth) acrylate and ditrimethylol propane tetra (meth) acrylate, are mentioned. Especially preferably, 1, 6- hexanediol di (meth) acrylate, a trimethylol propane tri (meth) acrylate, a trimethylol propane trioxyethyl (meth) acrylate, and a pentaerythritol tri (meth) acrylate are mentioned. have.
다음으로 (C)성분에 대하여 설명한다. Next, (C) component is demonstrated.
본 발명의 (C)성분으로서 사용되는 평균 입자경이 1∼100nm인 실리카 미립자(d)로서는, 규소를 함유하는 금속산화물이면서 평균 입경이 1∼100nm의 범위인 것이라면 특별히 제한되지 않는다. 실리카 미립자로서는 건조된 분말상의 실리카 미립자, 유기 용매에 분산된 콜로이달 실리카(실리카 졸)를 사용할 수 있다. 분산성의 점에서 유기 용매에 분산된 콜로이달 실리카(실리카 졸)를 사용하는 것이 바람직하다. 유기 용매에 분산된 콜로이달 실리카(실리카 졸)를 사용할 경우의 유기 용매로서는, 수지 조성물 중에 사용하는 유기 성분이 용해되는 것을 사용하는 것이 바람직하고, 예를 들면 알코올류, 케톤류, 에스테르류, 글리콜에테르류를 들 수 있다. 탈용매가 용이하다는 점에서 메탄올, 에탄올, 이소프로필알코올, 부틸알코올, n-프로필알코올 등의 알코올계, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤계의 유기 용매에 분산된 콜로이달 실리카, 실리카 졸, 실리카 미립자를 사용하는 것이 바람직하고, 더욱 바람직하게는 이소프로필알코올에 분산된 콜로이달 실리카이다. 특히 이소프로필알코올에 분산된 콜로이달 실리카를 사용했을 경우에는 탈용매 후의 점도가 다른 용제계에 비해 낮아, 점도가 낮은 수지 조성물을 안정적으로 제작하기에 적합하다. 이들 유기 용매에 분산된 콜로이달 실리카(실리카 졸), 실리카 미립자는 요구되는 특성을 극단적으로 해치지 않는 범위에서 실란 커플링제, 티타네이트계 커플링제 등의 커플링제로 표면 처리된 것이어도 되고, 유기 용매에 분산시키기 위해 계면활성제 등의 분산제를 사용하고 있는 것이어도 된다. The silica fine particles (d) having an average particle size of 1 to 100 nm used as the component (C) of the present invention are not particularly limited as long as they are metal oxides containing silicon and those having an average particle size of 1 to 100 nm. As silica fine particles, dried powdery silica fine particles and colloidal silica (silica sol) dispersed in an organic solvent can be used. In view of dispersibility, it is preferable to use colloidal silica (silica sol) dispersed in an organic solvent. As an organic solvent in the case of using colloidal silica (silica sol) dispersed in an organic solvent, it is preferable to use what melt | dissolves the organic component used in a resin composition, For example, alcohol, ketones, ester, glycol ether And the like. Colloidal silica and silica dispersed in an organic solvent of alcohols such as methanol, ethanol, isopropyl alcohol, butyl alcohol, n-propyl alcohol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, etc. It is preferable to use a sol and fine silica particles, more preferably colloidal silica dispersed in isopropyl alcohol. In particular, when colloidal silica dispersed in isopropyl alcohol is used, the viscosity after desolvent is lower than that of other solvent systems, and it is suitable for stably producing a resin composition having low viscosity. Colloidal silica (silica sol) and silica fine particles dispersed in these organic solvents may be surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent within the range of not impairing the required properties extremely. In order to disperse | distribute to, dispersing agents, such as surfactant, may be used.
실리카 미립자의 평균 입경은 1∼100nm가 바람직하고, 투명성과 유동성의 밸런스의 점에서 더욱 바람직하게는 1∼50nm, 보다 바람직하게는 5∼50nm, 가장 바람직하게는 5∼40nm이다. 1nm 미만이면, 제작한 수지 조성물의 점도가 극단적으로 증대되기 때문에, 실리카 미립자의 충전량이 제한되는 동시에 분산성이 악화되어 충분한 투명성, 선팽창계수를 얻을 수 없다. 또한 100nm를 넘으면 투명성이 현저하게 악화될 우려가 있으므로 바람직하지 않다. The average particle diameter of the silica fine particles is preferably 1 to 100 nm, more preferably 1 to 50 nm, more preferably 5 to 50 nm, and most preferably 5 to 40 nm in terms of the balance between transparency and fluidity. If it is less than 1 nm, since the viscosity of the produced resin composition increases extremely, the filling amount of silica fine particles will be limited and dispersibility will deteriorate, and sufficient transparency and coefficient of linear expansion cannot be obtained. If the thickness exceeds 100 nm, the transparency may be significantly deteriorated, which is not preferable.
여기서, 실리카 미립자의 평균 입자경은 질소흡착법(BET법)으로 구한 비표면적 S(㎡/g)로부터 D(nm)=2720/S의 식으로 계산된다. Here, the average particle diameter of silica fine particles is calculated by the formula of D (nm) = 2720 / S from specific surface area S (m <2> / g) calculated | required by the nitrogen adsorption method (BET method).
파장 400∼500nm의 광선투과율을 저하시키지 않기 위해 1차 입경이 200nm 이상인 실리카 미립자가 5% 이하의 비율로 존재하는 실리카 미립자를 사용하는 것이 바람직하고, 그 비율이 0%인 것이 보다 바람직하다. 실리카 미립자의 충전량을 올리기 위해 평균 입경이 다른 실리카 미립자를 혼합해서 사용해도 된다. 또한 실리카 미립자로서, 일본국 공개특허공보 평7-48117호에 나타나 있는 다공질 실리카 졸이나, 알루미늄, 마그네슘, 아연 등과 규소의 복합 금속산화물을 사용해도 된다. In order not to reduce the light transmittance of wavelength 400-500 nm, it is preferable to use the silica fine particle which exists in the ratio of 5% or less of silica fine particles whose primary particle diameter is 200 nm or more, and it is more preferable that the ratio is 0%. In order to raise the filling amount of a silica particle, you may mix and use the silica particle from which an average particle diameter differs. As the silica fine particles, the porous silica sol shown in JP-A-H7-48117 or a composite metal oxide of aluminum, magnesium, zinc, and silicon may be used.
경화성 수지 조성물 중의 실리카 미립자의 함유량은 15∼90wt%가 바람직하고, 선팽창계수와 경량화의 밸런스의 점에서 더욱 바람직하게는 25∼80wt%, 보다 바람직하게는 25∼70wt%, 가장 바람직하게는 30∼70wt%이다. 이 범위이면 유동성, 분산성이 양호하기 때문에 제조가 용이하고, 충분한 강도, 낮은 선팽창계수를 가지는 성형품을 제조할 수 있다. The content of the silica fine particles in the curable resin composition is preferably 15 to 90 wt%, more preferably 25 to 80 wt%, more preferably 25 to 70 wt%, most preferably 30 to 30 in terms of the balance between the coefficient of linear expansion and the weight reduction. 70wt%. If it is this range, since fluidity | liquidity and dispersibility are favorable, it will be easy to manufacture, and the molded article which has sufficient strength and low linear expansion coefficient can be manufactured.
본 발명의 경화성 수지 조성물은 상기 (A)성분, (B)성분 및 (C)성분을 필수 성분으로 하는데, 그 함유비율은 다음 범위가 바람직하다. 수지 조성물에 있어서 (A)성분 및 (B)성분의 합계에 대한 (A)성분의 배합량이 2∼83wt%, (B)성분의 배합량이 83∼2wt%, (C)성분의 배합량이 15∼90wt%이다. 보다 바람직하게는 (A)성분의 배합량이 5∼75wt%, (B)성분의 배합량이 80∼10wt%, (C)성분의 배합량이 15∼80wt%이다. 가장 바람직하게는 (A)성분의 배합량이 10∼65wt%, (B)성분의 배합량이 75∼15wt%, (C)성분의 배합량이 15∼70wt%이다. Curable resin composition of this invention makes said (A) component, (B) component, and (C) component an essential component, The content rate is preferable the following range. In the resin composition, the compounding amount of the component (A) to the total of the component (A) and the component (B) is 2 to 83 wt%, the compounding amount of the component (B) is 83 to 2 wt%, and the compounding amount of the component (C) is 15 to 90 wt%. More preferably, the compounding quantity of (A) component is 5-75 wt%, the compounding quantity of (B) component is 80-10 wt%, and the compounding quantity of (C) component is 15-80 wt%. Most preferably, the compounding quantity of (A) component is 10-65 wt%, the compounding quantity of (B) component is 75-15 wt%, and the compounding quantity of (C) component is 15-70 wt%.
본 발명의 경화성 수지 조성물은 (D)성분으로서 중합개시제, 바람직하게는 광중합 개시제를 포함하는 것이 좋다. 본 발명의 경화성 수지 조성물은 열중합이어도 성형, 경화가 가능하지만, 렌즈 등의 광학재료를 성형, 경화할 경우에는 엄밀하게 형상 제어 가능한 광경화가 유리하고, 그 때문에 광중합 개시제를 첨가하는 것이 바람직하게 된다. It is preferable that curable resin composition of this invention contains a polymerization initiator, Preferably a photoinitiator as (D) component. Although the curable resin composition of this invention can be shape | molded and hardened | cured even if it is thermal polymerization, when shape | molding and hardening optical materials, such as a lens, photocurable which can control shape strictly is advantageous, and therefore, it becomes preferable to add a photoinitiator. .
(D)성분으로서 사용되는 광중합 개시제로서는, 예를 들면 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인프로필에테르, 벤조인이소부틸에테르 등의 벤조인류; 아세토페논, 2,2-디에톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 2-하이드록시-2-메틸-페닐프로판-1-온, 디에톡시아세토페논, 1-하이드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온 등의 아세토페논류; 2-에틸안트라퀴논, 2-터샤리부틸안트라퀴논, 2-클로로안트라퀴논, 2-아밀안트라퀴논 등의 안트라퀴논류; 2,4-디에틸티오크산톤, 2-이소프로필티오크산톤, 2-클로로티오크산톤 등의 티오크산톤류; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류; 벤조페논, 4-벤조일-4'-메틸디페닐술파이드, 4,4'-비스메틸아미노벤조페논 등의 벤조페논류; 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 포스핀옥사이드류 등을 들 수 있다. As a photoinitiator used as (D) component, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propylether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 Acetophenones, such as -one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-teraryl butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; Thioxanthones, such as 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
이들은 단독 또는 2종 이상의 혼합물로서 사용할 수 있고, 나아가서는 트리에탄올아민, 메틸디에탄올아민 등의 제3급 아민, N,N-디메틸아미노안식향산 에틸에스테르, N,N-디메틸아미노안식향산 이소아밀에스테르 등의 안식향산 유도체 등의 촉진제 등과 조합시켜 사용할 수 있다. These can be used individually or as a mixture of 2 or more types, Furthermore, tertiary amines, such as a triethanolamine and a methyl diethanolamine, N, N- dimethylamino benzoic acid ethyl ester, N, N- dimethylamino benzoic acid isoamyl ester, etc. It can be used in combination with accelerators, such as a benzoic acid derivative.
한편 (D)성분으로서 사용되는 열중합개시제로서는 예를 들면 시클로헥사논퍼옥사이드, 3,3,5-트리메틸시클로헥사논퍼옥사이드, 메틸시클로헥사논퍼옥사이드 등의 케톤퍼옥사이드류; 1,1-비스(tert-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, 1,1-비스(tert-부틸퍼옥시)시클로헥산, n-부틸-4,4-비스(tert-부틸퍼옥시)발레레이트 등의 퍼옥시케탈류; 쿠멘하이드로퍼옥사이드, 2,5-디메틸헥산-2,5-디하이드로퍼옥사이드 등의 하이드로퍼옥사이드류; 1,3-비스(tert-부틸퍼옥시-m-이소프로필)벤젠, 2,5-디메틸-2,5-디(tert-부틸퍼옥시)헥산, 디이소프로필벤젠퍼옥사이드, tert-부틸쿠밀퍼옥사이드 등의 디알킬퍼옥사이드류; 데카노일퍼옥사이드, 라우로일퍼옥사이드, 벤조일퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드 등의 디아실퍼옥사이드류; 비스(tert-부틸시클로헥실)퍼옥시디카보네이트 등의 퍼옥시카보네이트류; tert-부틸퍼옥시벤조에이트, 2,5-디메틸-2,5-디(벤조일퍼옥시)헥산 등의 퍼옥시에스테르류 등의 유기 과산화물계 중합개시제 및 2,2'-아조비스이소부티로니트릴, 1,1-아조비스(시클로헥산-1-카르보니트릴), 아조쿠멘 2,2'-아조비스메틸발레로니트릴, 4,4'-아조비스(4-시아노길초산) 등의 아조계 중합개시제를 들 수 있다. On the other hand, examples of the thermal polymerization initiator used as the component (D) include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert- Peroxy ketals such as butyl peroxy) valerate; Hydroperoxides such as cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzeneperoxide, tert-butylco Dialkyl peroxides such as miper oxide; Diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; Peroxy carbonates such as bis (tert-butylcyclohexyl) peroxydicarbonate; organic peroxide-based polymerization initiators such as peroxy esters such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and 2,2'-azobisisobutyronitrile Azo systems such as 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2'-azobismethylvaleronitrile, and 4,4'-azobis (4-cyanogilacetic acid) And polymerization initiators.
이들 중합개시제의 사용량은 특별히 한정되는 것은 아니지만, 통상 (A)성분을 포함하는 중합성 성분의 합계량 100중량부에 기초하여 0.01∼25중량부인 것이 바람직하고, 0.05∼20중량부의 범위 내인 것이 더욱 바람직하다. 0.1∼15중량부의 범위 내인 것이 가장 바람직하다. Although the usage-amount of these polymerization initiators is not specifically limited, Usually, it is preferable that it is 0.01-25 weight part based on 100 weight part of total amounts of the polymeric component containing (A) component, It is more preferable to exist in the range of 0.05-20 weight part. Do. It is most preferable to exist in the range of 0.1-15 weight part.
본 발명의 경화성 수지 조성물이 상기 (A)성분, (B)성분, (C)성분 및 (D)성분을 포함할 경우, 그 바람직한 함유비율은 다음과 같다. (B)성분의 배합량은 (A)성분 100중량부에 대하여 5∼250중량부, 바람직하게는 20∼100중량부이다. (C)성분의 배합량은 (B)성분과 (A)성분의 배합량의 합계 100중량부에 대하여 0.1∼10중량부, 바람직하게는 1.0∼5중량부이다. When curable resin composition of this invention contains the said (A) component, (B) component, (C) component, and (D) component, the preferable content rate is as follows. The compounding quantity of (B) component is 5-250 weight part with respect to 100 weight part of (A) component, Preferably it is 20-100 weight part. The compounding quantity of (C) component is 0.1-10 weight part with respect to a total of 100 weight part of the compounding quantity of (B) component and (A) component, Preferably it is 1.0-5 weight part.
다른 관점에서는 경화성 수지 조성물 중에 (A)성분, (B)성분 및 (D)성분의 합계 100wt%에 대하여 (D)성분: 0.1∼10wt%를 함유하는 것이 좋다. (A)성분, (B)성분 및 (D)성분의 합계에 대하여 (D)성분의 배합비율이 상기의 범위 내에 있음으로 인해, 상승적으로 이형성이나 경화성에 보여지는 성형성과, 내열성 및 광학특성과의 특성 밸런스가 개선된다. 또한 (D)성분이 너무 적으면 경화 부족이 생기기 쉬우며 내열성이나 내광성이 저하하고, 너무 많으면 기계적 강도가 저하하거나 내열성이 저하하거나 한다. 또한 경화성 수지 조성물 중에 유기 용제 및 필러를 포함할 경우, 상기 함유량은 이들을 제외하고 계산된다. From another viewpoint, it is good to contain (D) component: 0.1-10 wt% with respect to a total of 100 wt% of (A) component, (B) component, and (D) component in curable resin composition. Since the compounding ratio of (D) component with respect to the sum total of (A) component, (B) component, and (D) component is in the said range, the moldability, heat resistance, and optical characteristic which are synergistically exhibited in releasability and curability are The characteristic balance of is improved. In addition, when there are too few (D) components, hardening shortage will arise easily and heat resistance and light resistance will fall, and when too much, mechanical strength will fall or heat resistance will fall. Moreover, when an organic solvent and a filler are included in curable resin composition, the said content is calculated except these.
본 발명의 경화성 수지 조성물 중에는 수지 조성물 제작시에 중합 반응이 진행되어 점도가 상승하는 것을 막을 목적으로 중합 금지제를 함유시켜도 된다. 또한 본 발명의 경화성 수지 조성물 중에는 흡수율을 저감시킬 목적으로 트리메틸메톡시실란, 헥사메틸디실라잔(hexamethyldisilazane), 트리메틸클로로실란, 옥타메틸시클로테트라실록산 등의 소수화(疎水化) 처리제를 함유시켜도 된다. The curable resin composition of this invention may contain a polymerization inhibitor for the purpose of preventing a polymerization reaction from advancing and a viscosity increase at the time of resin composition preparation. In addition, the curable resin composition of this invention may contain hydrophobization treatment agents, such as a trimethylmethoxysilane, hexamethyldisilazane, a trimethylchlorosilane, and an octamethylcyclo tetrasiloxane, in order to reduce water absorption.
본 발명의 경화성 수지 조성물 중에는 필요에 따라서 투명성, 내용제성, 내액정성, 내열성 등의 특성을 해하지 않는 범위에서 열가소성 또는 열경화성의 올리고머나 폴리머를 병용할 수 있다. 이 경우, 흡수성을 저감시키거나 또한 선팽창계수를 저감시키는 등의 목적도 겸해, 지환식 구조나 카르도 골격을 가지는 올리고머나 폴리머를 사용하는 것이 바람직하다. In the curable resin composition of this invention, a thermoplastic or thermosetting oligomer and a polymer can be used together as needed in the range which does not impair the characteristics, such as transparency, solvent resistance, liquid crystal resistance, and heat resistance. In this case, it is also desirable to use an oligomer or polymer having an alicyclic structure or a cardo skeleton, which also serves as a purpose of reducing water absorption or reducing the coefficient of linear expansion.
또한 본 발명의 경화성 수지 조성물 중에는 필요에 따라서 투명성, 내용제성, 내액정성, 내열성 등의 특성을 해하지 않는 범위에서 소량의 산화 방지제, 자외선 흡수제, 염안료, 다른 무기 필러 등의 충전제 등을 포함하고 있어도 된다. Furthermore, the curable resin composition of the present invention may contain a small amount of fillers such as antioxidants, ultraviolet absorbers, dyes, and other inorganic fillers in a range that does not impair the properties such as transparency, solvent resistance, liquid crystal resistance, and heat resistance, if necessary. do.
본 발명의 경화성 수지 조성물을 제조하는 방법으로서는, 예를 들면 유기 용매에 분산된 콜로이달 실리카(실리카 졸)와 그 밖의 배합물을 혼합하고, 필요에 따라 교반하면서 감압함으로써 유기 용매를 제거하는 방법, 유기 용매에 분산된 콜로이달 실리카(실리카 졸)와 그 밖의 배합물을 혼합하고, 필요에 따라서 탈용매한 후 캐스트하고 또 탈용매시키는 방법, 분산능력이 높은 혼합장치를 이용해서 건조한 분말상의 실리카 미립자를 분산시키는 방법 등을 들 수 있다. 분산능력이 높은 장치로서는 예를 들면 토쿠슈키카코교(주) 제품인 필믹스나 각종 비즈밀 등을 들 수 있다. 분산능력이 높은 장치를 사용할 때에는 혼합 또는 혼련 중에 반응이 급속히 진행되지 않도록, 온도가 지나치게 상승하지 않게 주의할 필요가 있다. 경화성 수지 조성물을 제작할 때의 조성물의 온도는 30∼100℃로 유지하는 것이 바람직하고, 탈용매 스피드와의 밸런스의 점에서 더욱 바람직하게는 35∼70℃, 가장 바람직하게는 35∼60℃이다. 온도를 너무 올리면, 유동성이 극단적으로 저하하거나 겔형상이 되어버려 시트화할 수 없게 된다. 또한 분산능력이 높은 장치를 사용할 경우에는 장치의 마모 등에 의한 불순물의 혼입에 주의할 필요가 있다. 유기 용매에 분산된 콜로이달 실리카를 이용할 경우, 이 유기 용매를 경화성 수지 조성물 중에 잔존시켜도 된다. 유기 용매를 함유시킬 경우, 열처리 등의 후처리 공정을 마련하여, 최종적으로 예를 들면 광학 필름·시트형상의 본 발명의 경화성 수지 조성물로 이루어지는 코팅층으로부터 유기 용매를 탈리시키면 된다. 유기 용매의 경화성 수지 조성물 중에 있어서의 함유량은 가교 공정이나 열처리 등에 의해 휘발 성분을 제거하는 공정에서, 발포되거나 시트에 주름이 발생하거나 착색하는 등의 문제를 회피하기 위해서는 경화성 수지 조성물의 0∼10wt%가 바람직하고, 더욱 바람직하게는 0∼5wt%이며, 가장 바람직하게는 0∼3wt%이다. As a method of manufacturing curable resin composition of this invention, the colloidal silica (silica sol) disperse | distributed to the organic solvent, and the other compound are mixed, and the method of removing an organic solvent by pressure-reducing, stirring as needed, organic The colloidal silica (silica sol) dispersed in the solvent and other blends are mixed, and if necessary, desolvated, cast and desolvented, and dry powdery silica fine particles are dispersed using a high dispersing mixing device. And the like. As a device with high dispersibility, the peel mix, various bead mills, etc. which are manufactured by Tokushuki Kakogyo Co., Ltd. are mentioned, for example. When using a device with high dispersibility, care must be taken not to increase the temperature excessively so that the reaction does not proceed rapidly during mixing or kneading. It is preferable to maintain the temperature of the composition at the time of producing curable resin composition at 30-100 degreeC, More preferably, it is 35-70 degreeC, Most preferably, it is 35-60 degreeC from the point of balance with a desolvent speed. If temperature is raised too much, fluidity | liquidity will fall extremely or it will become a gel shape and it will become unable to form a sheet. In addition, when using a device with high dispersibility, attention should be paid to the incorporation of impurities due to wear and the like of the device. In the case of using colloidal silica dispersed in an organic solvent, the organic solvent may be left in the curable resin composition. What is necessary is just to provide post-treatment processes, such as heat processing, when it contains an organic solvent, and to finally remove an organic solvent from the coating layer which consists of curable resin composition of this invention of an optical film sheet form, for example. The content of the organic solvent in the curable resin composition is 0 to 10% by weight of the curable resin composition in order to avoid problems such as foaming, wrinkles on the sheet, or coloring in the step of removing the volatile components by a crosslinking process, heat treatment or the like. Is preferable, More preferably, it is 0-5 wt%, Most preferably, it is 0-3 wt%.
본 발명의 경화성 수지 조성물은 자외선 등의 활성 에너지선을 조사함으로써 경화물을 얻을 수 있다. 여기서 활성 에너지선을 조사하여 경화할 경우에 이용되는 광원의 구체예로서는, 예를 들면 크세논 램프, 카본 아크, 살균등, 자외선용 형광등, 복사용 고압 수은등, 중압 수은등, 고압 수은등, 초고압 수은등, 무전극 램프, 메탈 할라이드 램프, 혹은 주사형, 커튼형 전자선 가속로에 의한 전자선 등을 들 수 있다. 또한 본 발명의 경화성 수지 조성물을 자외선 조사에 의해 경화할 경우, 경화에 필요한 자외선 조사량은 300∼20000mJ/c㎡ 정도이면 된다. 또한 경화성 수지 조성물을 충분히 경화하기 위해, 질소가스 등의 불활성 가스 분위기 중에서 자외선 등의 활성 에너지선을 조사하는 것이 바람직하다. Curable resin composition of this invention can obtain hardened | cured material by irradiating active energy rays, such as an ultraviolet-ray. As a specific example of the light source used when irradiating and hardening an active energy ray here, xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high pressure mercury lamp for radiation, a high pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an electrode Lamps, metal halide lamps, or electron beams by scanning or curtain-type electron beam accelerators. Moreover, when hardening curable resin composition of this invention by ultraviolet irradiation, the ultraviolet irradiation amount required for hardening may be about 300-20000mJ / cm <2>. Moreover, in order to fully harden curable resin composition, it is preferable to irradiate active energy rays, such as an ultraviolet-ray, in inert gas atmospheres, such as nitrogen gas.
또한 본 발명의 경화성 수지 조성물은 가열함으로써도 경화물을 얻을 수 있다. 경화 온도로서는 70∼200℃가 바람직하다. 보다 바람직하게는 80∼180℃이다. 경화 시간으로서는 1분∼15시간이 바람직하다. 보다 바람직하게는 3분∼10시간이다. Moreover, hardened | cured material can also be obtained by heating curable resin composition of this invention. As hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-180 degreeC. As hardening time, 1 minute-15 hours are preferable. More preferably, they are 3 minutes-10 hours.
활성 에너지선에 의한 경화 및/또는 열중합에 의한 가교 후에 고온으로 열처리할 경우에는 그 열처리 공정 중에 선팽창계수를 저감하는 등의 목적으로, 질소분위기하 또는 진공상태로 150℃∼300℃, 1∼24시간의 열처리 공정을 포함시키는 것이 바람직하다. When heat treatment at high temperature after curing by active energy rays and / or crosslinking by thermal polymerization is carried out at a temperature of 150 ° C. to 300 ° C. under a nitrogen atmosphere or in a vacuum state for the purpose of reducing the coefficient of linear expansion during the heat treatment step. It is desirable to include a 24 hour heat treatment process.
또한 본 발명의 경화성 수지 조성물은 필요에 따라 실란 커플링제, 중합 금지제, 레벨링제, 표면 윤활제, 소포제, 광안정제, 산화 방지제, 가소제, 대전 방지제, 충전제 등의 첨가제를 병용할 수 있다. Moreover, curable resin composition of this invention can use together additives, such as a silane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoamer, a light stabilizer, antioxidant, a plasticizer, an antistatic agent, and a filler.
본 발명의 경화성 수지 조성물의 경화물은 통상의 방법에 따라 자외선, 가시광 레이저 등의 활성 에너지선을 조사함으로써 얻을 수 있다. 자외선을 사용할 경우, 저압 또는 고압 수은등, 초고압 수은등, 메탈 할라이드 램프, 크세논등 등을 이용해서 조사한다. 특히 광원으로서는 350∼450nm에 에너지 강도가 강한 램프가 바람직하다. The hardened | cured material of curable resin composition of this invention can be obtained by irradiating active energy rays, such as an ultraviolet-ray and a visible light laser, in accordance with a conventional method. When using ultraviolet rays, irradiation is performed using low or high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, and xenon lamps. In particular, as a light source, a lamp having a high energy intensity at 350 to 450 nm is preferable.
자외선 등의 활성 에너지선 혹은 열에 의해 경화시켜서 얻어지는 본 발명의 경화성 수지 조성물의 경화물의 굴절률은 25℃에서 1.45 이상인 것이 바람직하고, 보다 바람직하게는 25℃에서 1.48 이상이다. 특히 본 발명의 광학재료용 수지 조성물로 광학 렌즈를 제작할 경우, 경화물의 굴절률이 25℃에서 1.45 미만이면 충분한 렌즈 모듈을 콤팩트한 사이즈로 할 수 없다는 문제가 생기는 경우가 있다. It is preferable that the refractive index of the hardened | cured material of the curable resin composition of this invention obtained by making it harden | cure by active energy rays, such as an ultraviolet-ray, is 1.45 or more at 25 degreeC, More preferably, it is 1.48 or more at 25 degreeC. When manufacturing an optical lens with the resin composition for optical materials of this invention especially, when the refractive index of hardened | cured material is less than 1.45 at 25 degreeC, a problem may arise that a sufficient lens module cannot be made into a compact size.
또한 경화물의 아베수(빛의 파장에 따라 그 굴절률을 바꾸는 성질을 규정하는 물질 고유의 수치)는 40.0 이상인 것이 바람직하고, 보다 바람직하게는 45.0 이상이다. 경화물의 아베수가 40.0 미만이면 색수차가 커 색의 번짐이 발생하기 때문에 바람직하지 않다. Moreover, it is preferable that the Abbe number of the hardened | cured material (the numerical value inherent in the substance which defines the characteristic which changes the refractive index with respect to the wavelength of light) is 40.0 or more, More preferably, it is 45.0 or more. If the Abbe number of the cured product is less than 40.0, chromatic aberration is large and color bleeding occurs, which is not preferable.
본 발명의 경화성 수지 조성물을 성형, 경화하여 얻어지는 복합체 경화물은 렌즈나 프리즘 등의 광학재료로서 뛰어나다. 특히 비구면(非球面) 렌즈, 프레넬 렌즈(fresnel lense), 렌티큘러 렌즈(lenticular lense), 안경 렌즈 등의 광학 플라스틱 렌즈, 및 광학 필름용 코팅재료나 광학 접착재료로서 유용하다. 그리고 본 발명의 경화성 수지 조성물로부터 얻어지는 광학 렌즈는 촬상장치에 유리하게 사용된다. 또한 경화성 수지 조성물 또는 복합체 경화물은 그 밖에도 광디스크, 광섬유, 광도파로 등의 광전자 공학(optoelectronics)용 용도, 인쇄 잉크, 도료, 클리어 코팅제, 광택 니스 등에도 사용할 수 있다.The composite hardened | cured material obtained by shape | molding and hardening curable resin composition of this invention is excellent as optical materials, such as a lens and a prism. In particular, it is useful as optical plastic lenses, such as an aspherical lens, a fresnel lens, a lenticular lens, a spectacle lens, and a coating material or optical adhesive material for optical films. And the optical lens obtained from curable resin composition of this invention is used advantageously for an imaging device. Curable resin compositions or cured composites can also be used for optoelectronics such as optical discs, optical fibers, optical waveguides, printing inks, paints, clear coatings, gloss varnishes, and the like.
또한 본 발명의 경화성 수지 조성물을 접착제로서 사용할 수도 있고, 이것이 경화하여 생기는 경화물을 접착층으로서 가지는 물품으로서는, 예를 들면 휴대전화, 휴대 게임기, 디지털 카메라 등이 있다. Moreover, the curable resin composition of this invention can also be used as an adhesive agent, and the article which has the hardened | cured material which hardens | generates by this as an adhesive layer is a mobile telephone, a portable game machine, a digital camera, etc., for example.
본 발명의 경화성 수지 조성물을 이용해서 편광 필름과 보호판을 접합할 때에는 예를 들면, 활성 에너지선 투과성이 뛰어난 무알칼리 유리제나 석영 유리제 등의 보호판에 제한되지 않고, 자외선 흡수가 큰 아크릴판, 폴리카보네이트 등의 보호판이라도, 상기 조성물의 양호한 반응 경화성으로 인해 사용 가능하다. When joining a polarizing film and a protective plate using the curable resin composition of this invention, it is not limited to the protective plates, such as an alkali free glass and quartz glass which are excellent in active energy ray permeability, for example, The acryl plate and polycarbonate which have large ultraviolet absorption Even protective plates, such as these, can be used because of the favorable reaction curability of the composition.
본 발명의 경화성 수지 조성물은 편광 필름 등의 기재에 롤코터, 스핀코터, 스크린 인쇄법 등의 도공장치를 이용해서 접착제 막두께가 1∼100㎛가 되도록 도포하고, 보호판을 접합하여 자외선을 보호판 위에서 조사하여 경화함으로써 접착시킬 수 있다. The curable resin composition of this invention is apply | coated so that adhesive film thickness may be 1-100 micrometers to base materials, such as a polarizing film, using a roll coater, a spin coater, a screen printing method, etc., a protective plate is bonded, and an ultraviolet-ray is used on a protective plate. It can bond by irradiating and hardening.
<실시예><Examples>
다음으로 실시예에 의해 본 발명을 설명하지만, 본 발명은 이들에 의해 제한되는 것은 아니다. 또한 각 예 중의 부는 모두 중량부이다. 또한 실시예 중의 연화온도 등의 측정은 이하에 나타내는 방법에 의해 시료 조제 및 측정을 행하였다. Next, although an Example demonstrates this invention, this invention is not restrict | limited by these. In addition, all the parts in each case are a weight part. In addition, the measurement of the softening temperature etc. in the Example performed sample preparation and the measurement by the method shown below.
1)폴리머의 분자량 및 분자량 분포 1) Molecular weight and molecular weight distribution of polymer
공중합체의 분자량 및 분자량 분포 측정은 GPC(토소 제품, HLC-8120GPC)를 사용하고, 용매:테트라하이드로푸란(THF), 유량:1.0ml/min, 칼럼온도:40℃로 행하였다. 공중합체의 분자량은 단분산 폴리스티렌에 의한 검량선을 이용하여, 폴리스티렌 환산 분자량으로서 측정하였다. The molecular weight and molecular weight distribution of the copolymer were measured using a solvent-containing tetrahydrofuran (THF), a flow rate: 1.0 ml / min, and a column temperature of 40 ° C. using GPC (TOSO, HLC-8120GPC). The molecular weight of the copolymer was measured as a polystyrene reduced molecular weight using a calibration curve by monodisperse polystyrene.
2)폴리머의 구조 및 가용성 시험 2) Polymer structure and solubility test
니혼덴시 제품 JNM-LA600형 핵자기공명 분광장치를 이용해서, 13C-NMR 및 1H-NMR 분석에 의해 결정하였다. 용매로서 클로로포름-d1을 사용하고, 테트라메틸실란의 공명선을 내부 표준으로서 사용하였다. It was determined by 13C-NMR and 1H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by Nippon Denshi. Chloroform-d1 was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard.
가용성 시험은 25℃의 각종 유기 용매(톨루엔, 크실렌, 테트라하이드로푸란, 디클로로에탄 및 클로로포름) 100ml에 대하여 공중합체 1g을 첨가하고, 자석 교반기(magnetic stirrer)를 이용해서 30분 교반한 후에 육안으로 용해성을 확인하였다. 상기 유기 용매 어느 것에도 전부 용해되고, 겔의 생성이 인정되지 않는 경우를 용해성:○로 하였다. The solubility test was performed by adding 1 g of a copolymer to 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane and chloroform) at 25 ° C., stirring it for 30 minutes using a magnetic stirrer, and then visually dissolving it. It was confirmed. It melt | dissolved in all the said organic solvents, and the case where the formation | generation of a gel is not recognized was made into solubility: (circle).
3)유리전이온도(Tg) 및 연화온도 측정의 시료 조제 및 측정 3) Sample preparation and measurement of glass transition temperature (Tg) and softening temperature measurement
공중합체 용액을 유리 기판에 건조한 후의 두께가 20㎛가 되도록 균일하게 도포한 후, 핫플레이트를 이용해서 90℃로 30분간 가열하고 건조시켰다. 얻어진 유리 기판상의 수지막은 유리 기판과 함께, TMA(열기계 분석장치) 측정장치에 세팅하고, 질소기류하, 승온속도 10℃/분으로 220℃까지 승온하고, 또한 220℃로 20분간 가열 처리함으로써 수지를 경화하였다. 유리 기판을 실온까지 식힌 후, TMA 측정장치 중의 시료에 분석용 프로브를 접촉시켜 질소기류하, 승온속도 10℃/분으로 30℃에서 360℃까지 스캔시킴으로써 측정을 실시하고, 접선법으로 연화온도를 구하였다. 샘플의 내열성으로 인해, 프로브가 수지막을 관통하지 않아 막두께보다도 작은 프로브 침입량을 나타내지 않을 경우에는 연화온도 외에, 프로브가 침입한 온도와 막두께에 대한 침입량을 백분율로 표시하였다. After apply | coating a copolymer solution uniformly so that the thickness after drying to a glass substrate might be set to 20 micrometers, it heated at 90 degreeC for 30 minutes using a hotplate, and dried. The resin film on the obtained glass substrate was set to a TMA (thermomechanical analyzer) measuring apparatus with a glass substrate, and it heated up to 220 degreeC by 10 degree-C / min of temperature increase rate under nitrogen stream, and heat-processed at 220 degreeC for 20 minutes. The resin was cured. After the glass substrate has cooled to room temperature, the sample in the TMA measuring apparatus is brought into contact with an analytical probe and measured by scanning from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min under a nitrogen stream, and the softening temperature is tangentially determined. Obtained. When the probe did not penetrate the resin film and did not exhibit a probe penetration amount smaller than the film thickness due to the heat resistance of the sample, in addition to the softening temperature, the penetration amount with respect to the temperature at which the probe entered and the film thickness was expressed as a percentage.
4)열중량 감소량 및 내열변색성의 측정 4) Determination of heat weight loss and heat discoloration resistance
공중합체의 열분해온도 및 내열변색성의 측정은 시료를 TGA(열천칭) 측정장치에 세팅하고, 질소기류하, 승온속도 10℃/분으로 30℃에서 320℃까지 스캔시킴으로써 측정을 실시하고, 300℃에서의 중량 감소량을 구함과 동시에 측정 후의 시료의 변색량을 육안으로 확인하여 ◎:열변색 없음, ○:담황색, △:갈색, ×:흑색으로 분류함으로써 내열변색성을 평가하였다. The thermal decomposition temperature and heat discoloration resistance of the copolymer were measured by setting the sample in a TGA (thermobalance) measuring apparatus and scanning the sample at 30 ° C. to 320 ° C. at a temperature rising rate of 10 ° C./min under nitrogen stream, and 300 ° C. Heat discoloration resistance was evaluated by dividing the amount of weight loss in the sample and visually confirming the amount of discoloration of the sample after measurement by dividing it into?: No heat discoloration,?: Pale yellow,?
5)흡수율의 측정 5) Measurement of Absorption Rate
60℃로 24시간 진공 건조한 테스트 샘플(경화 시트)의 무게를 Wo로 하고, 그것을 ±0.1mg까지 측정 가능한 저울로 칭량하여 온도:85℃, 상대습도:85%의 항온항습조 내에서 1주일간 가습하였다. 가습 후 테스트 샘플에 묻은 물기를 닦아내고, 샘플을 ±0.1mg까지 측정 가능한 저울로 칭량하여 W로 하였다. 하기의 식(3)으로 흡수율을 산출하였다. 같은 테스트 샘플을 3개 준비하여 동일하게 시험하였다. Weigh the test sample (cured sheet) vacuum dried at 60 ° C. for 24 hours and weigh it with a scale that can measure up to ± 0.1 mg, and humidify for 1 week in a constant temperature and humidity chamber with a temperature of 85 ° C. and a relative humidity of 85%. It was. After moisturizing, the water on the test sample was wiped off, and the sample was weighed on a scale capable of measuring up to ± 0.1 mg to obtain W. Absorption rate was computed by following formula (3). Three identical test samples were prepared and tested identically.
Wo/W×100=흡수율 (3) Wo / W × 100 = absorption rate (3)
6)내용제성의 측정 6) Measurement of solvent resistance
공중합체의 내용제성의 측정은 200℃ 1시간 진공 프레스 성형한 시료판을 톨루엔에 실온에서 10분간 침지하고, 침지 후의 시료의 변화를 육안으로 확인하여 ○:변화없음, △:팽윤, ×:변형·팽창으로 분류함으로써 내용제성을 평가하였다. The solvent resistance of the copolymer was immersed in toluene for 10 minutes at room temperature in a sample plate subjected to vacuum press molding at 200 ° C. for 1 hour, and the change of the sample after immersion was visually observed. Solvent resistance was evaluated by classifying by expansion.
7)굴절률의 측정 7) measurement of refractive index
합성한 가용성 다관능 (메타)아크릴산에스테르 공중합체를 톨루엔에 용해하고, 그것에 개시제로서 퍼부틸 O를 가용성 다관능 (메타)아크릴산에스테르 공중합체 100중량부에 대하여 1.0중량부 첨가하였다. 이 중합체 용액으로부터 캐스트 시트를 작성하고, 이 캐스트 시트를 파쇄해 펠렛화하여 프레스 금형에 충전하고, 170℃로 1시간, 프레스 성형기로 경화시켰다. 얻어진 경화된 평행 평판을 테스트 피스로 해서, KPR-200(시마즈 칼뉴(shimadzu kalnew)사 제품)으로 d선(587.6nm)의 굴절률을 측정하였다. 측정 타이밍은 성형 직후 85℃×85RH의 습열 조건의 고온고습기에 1주일간 투입한 후로 하였다. The synthesized soluble polyfunctional (meth) acrylic acid ester copolymer was dissolved in toluene, and 1.0 parts by weight of perbutyl O was added to 100 parts by weight of the soluble polyfunctional (meth) acrylic acid ester copolymer. The cast sheet was created from this polymer solution, the cast sheet was crushed and pelletized, filled into a press die, and cured with a press molding machine at 170 ° C for 1 hour. Using the obtained hardened parallel plate as a test piece, the refractive index of d line (587.6 nm) was measured by KPR-200 (made by Shimadzu Kalnew). The measurement timing was made into 1 week after putting into the high temperature and high humidity of 85 degreeC * 85RH wet heat conditions immediately after shaping | molding.
8)밀착성 시험 8) adhesion test
공중합체를 용제(메틸에틸케톤)로 희석한 바니쉬(varnish)를 유리 기판상에 도포하여 80℃로 5분간 건조시킨 후, 이너트 오븐(inert oven) 안에서 질소기류하 200℃, 1시간 경화하였다. 다음으로 공중합체의 경화된 도막이 올려진 유리 기판을 JIS K 5400에 따라, 도막의 표면에 1mm 간격으로 세로, 가로 11개의 절개선을 넣어 100개의 바둑판눈금을 만들었다. 셀로판 테이프를 그 표면에 밀착시킨 후, 한번에 벗겼을 때에 박리되지 않고 잔존한 매스눈금(grid)의 개수를 세었다. Varnish diluted with a solvent (methyl ethyl ketone) was applied onto a glass substrate, dried at 80 ° C. for 5 minutes, and then cured at 200 ° C. under nitrogen stream for 1 hour in an inert oven. . Next, according to JIS K 5400, the glass substrate on which the cured coating film of the copolymer was put was put in 11 vertical incision lines at 1 mm intervals on the surface of the coating film to make 100 checker scales. After the cellophane tape was brought into close contact with the surface, the number of mass grids remaining without peeling off at one time was counted.
9)경화성 수지 조성물의 물성 측정용 시험편의 작성9) Preparation of test piece for physical property measurement of curable resin composition
폭 50mm, 길이 50mm, 두께 1.0mm의 2장의 유리판 사이를 0.2∼1.0mm의 틈을 두고 바깥둘레를 폴리이미드 테이프로 감아 고정한 유리틀에 경화성 조성물을 주입하고, 1) 이 유리틀의 한 면으로부터 상술한 고압 수은 램프로 5초간 자외선을 조사하거나, 혹은 2) 이 유리틀을 질소가스 기류하의 이너트 가스 오븐에 넣고 180℃로 1시간 가열함으로써 경화시켰다. 유리틀로부터 경화된 수지판을 탈형(脫型)하여 각종 물성 측정에 사용하였다. The curable composition is injected into a glass frame which is wound around two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm with a gap of 0.2 to 1.0 mm and fixed with polyimide tape, and then 1) from one side of this glass frame. Ultraviolet rays were irradiated for 5 seconds with the above-mentioned high pressure mercury lamp, or 2) this glass mold was hardened by heating in 180 degreeC for 1 hour in the inner gas oven under nitrogen gas stream. The resin plate cured from the glass frame was demolded and used for measuring various physical properties.
10)굴절률의 측정 10) Measurement of refractive index
아베 굴절률계(아타고(주) 제품)로 589nm에서의 굴절률 및 아베수를 측정하였다. The refractive index and Abbe number in 589 nm were measured with the Abbe refractometer (Atago Co., Ltd. product).
11)색상(YI) 11) Color (YI)
두께 1.0mm의 평판을 색채색차계(상품명 'MODEL TC-8600', 도쿄덴쇼쿠(주) 제품')로 측정하고 그 YI값을 나타냈다. A flat plate having a thickness of 1.0 mm was measured with a color difference meter (brand name 'MODEL TC-8600', manufactured by Tokyo Denshoku Co., Ltd.), and the YI value thereof was shown.
12)Haze(탁도) 및 전광선투과율 Haze (turbidity) and total light transmittance
0.2mm 두께의 테스트 피스를 제작하고, 샘플의 Haze(탁도)와 전광선투과율을 적분구식 광선투과율 측정장치(닛폰덴쇼쿠사 제품, SZ-∑90)를 이용해서 측정하였다. A 0.2 mm-thick test piece was produced, and the Haze (turbidity) and total light transmittance of the sample were measured using an integrated sphere light transmittance measuring apparatus (SZ-∑90, manufactured by Nippon Denshoku Co., Ltd.).
13)이형성: 경화한 수지를 틀에서 이형시켰을 때의 난이도에 따라 평가하였다. 13) Release property: The cured resin was evaluated according to the difficulty of releasing the mold from the mold.
○ … 틀에서의 이형성이 양호 ○…. Good mold release
△ … 이형이 다소 곤란 Δ. Molding is somewhat difficult
× … 이형이 곤란 혹은 틀 잔류가 있음×… Mold release is difficult or mold remains
14)틀 재현성: 경화된 수지층의 표면형상과 틀의 표면형상을 관찰하였다. 14) Frame reproducibility: The surface shape of the cured resin layer and the surface shape of the frame were observed.
○ … 재현성 양호 ○…. Good reproducibility
△ … 경화의 조건(빛, 열)에 따라서는 재현성이 양호 Δ. Good reproducibility depending on curing conditions (light and heat)
× … 재현성이 불량 ×… Poor reproducibility
15)버(burr), 누설: 경화된 수지를 금형으로부터 이형시켰을 때에 성형품의 제품부분 이외에 발생한 버의 크기 및 틀의 클리어런스(clearance)에의 수지의 새어들어감의 정도에 따라 평가하였다. 15) Burr, Leakage: The cured resin was evaluated according to the size of the burr generated in addition to the product part of the molded article when the cured resin was released from the mold and the degree of leakage of the resin to the clearance of the mold.
○ … 버의 생성량이 0.05mm 미만, 틀 클리어런스에의 수지의 새어들어간 정도가 1.0mm 미만. ○…. The amount of burr produced is less than 0.05 mm, and the degree of leakage of the resin to the frame clearance is less than 1.0 mm.
△ … 버의 생성량이 0.05mm 이상, 0.2mm 미만. 틀 클리어런스에의 수지의 새어들어간 정도가 1.0mm 이상, 3.0mm 미만. Δ. The amount of burr produced is not less than 0.05 mm and less than 0.2 mm. The leaking degree of resin to a frame clearance is less than 1.0mm, less than 3.0mm.
× … 버 생성량이 0.2mm 이상, 틀 클리어런스에의 수지의 새어들어간 정도가 3.0mm 이상. ×… Burr formation amount is more than 0.2mm, and degree of resin leak to frame clearance is more than 3.0mm.
16)리플로우 내열성: 1mm 두께의 평행 평판을 테스트 피스로 하고, 분광측색계 CM-3700d(코니카미놀타사 제품)로 파장:400nm의 분광 투과율을 측정하였다. 측정 타이밍은 190℃ 60분에서의 포스트 큐어를 실시한 내열 시험 전과, 에어 오븐 중 260℃, 8분간의 내열 시험 후로 하였다. 16) Reflow heat resistance: The 1-mm-thick parallel plate was used as the test piece, and the spectral transmittance of wavelength: 400 nm was measured with the spectrophotometer CM-3700d (made by Konica Minolta). The measurement timing was made before the heat test which performed postcure at 190 degreeC 60 minutes, and after the heat test for 8 minutes at 260 degreeC in an air oven.
17)내(耐)히트사이클성 17) Heat cycle resistance
157mW의 초고압 수은등을 이용해서 3000mJ의 에너지로 무알칼리 유리(두께; 0.7mm)와 2mm 두께의 아크릴판을 25㎛의 두께로 접착시킨 샘플을 1사이클, -35℃로 30분, 85℃로 30분의 조건으로 100사이클 행한 후, 2장의 기판의 박리 모양을 관찰하여 박리 없음을 ○, 박리 있음을 ×로 평가하였다. Using a 157mW ultra-high pressure mercury lamp, a sample bonded by alkali-free glass (thickness; 0.7mm) and 2mm-thick acrylic plate with a thickness of 25µm with energy of 3000mJ was cycled for 30 minutes at -35 ° C for 30 minutes at 30 ° C at 85 ° C. After performing 100 cycles on the conditions of minutes, the peeling pattern of two board | substrates was observed, and (circle) and no peeling were evaluated as (x).
18)내습성 18) moisture resistance
157mW의 초고압 수은등을 이용해서 3000mJ의 에너지로 무알칼리 유리(두께; 0.7mm)와 2mm 두께의 아크릴판을 25㎛의 두께로 접착시킨 샘플을 60℃, 90%RH에 100시간 방치한 후의 2장의 기판의 박리 모습을 관찰하여 박리 없음을 ○, 박리 있음을 ×로 평가하였다. Two pieces of samples after leaving an alkali-free glass (thickness; 0.7 mm) and a 2 mm thick acrylic plate bonded to a thickness of 25 µm using an ultra-high pressure mercury lamp of 157 mW at 25 m thickness for 100 hours at 60 ° C and 90% RH. The peeling state of the board | substrate was observed, and (circle) and no peeling were evaluated as (x).
19)형상유지 내열성 19) Shape keeping heat resistance
경화시켜, 포스트 큐어를 실시한 복합체 경화물층의 구면 렌즈의 표면형상(형상 1)과, 280℃의 솔더 리플로우로를 3회 통과시킨 후의 복합체 경화물층의 구면 렌즈의 표면형상(형상 2)을 미타카코우키 가부시키가이샤 제품 비접촉 삼차원형상 측정장치로 측정하여, 형상 1과 형상 2의 차이의 최대값을 형상유지 내열성으로서 산출하였다. The surface shape (shape 1) of the spherical lens of the composite hardened | cured material layer which hardened and post-cured, and the surface shape of the spherical lens of the composite hardened | cured material layer after passing through the solder reflow furnace of 280 degreeC 3 times (shape 2). Was measured with a non-contact three-dimensional shape measuring apparatus manufactured by Mitaka Kouki Co., Ltd., and the maximum value of the difference between the shape 1 and the shape 2 was calculated as shape holding heat resistance.
(실시예 1)(Example 1)
디메틸올트리시클로데칸디아크릴레이트 3.2몰(926.5ml), 이소보닐메타크릴레이트 8.0몰(1814.1ml), 2-하이드록시프로필메타크릴레이트 4.8몰(645.5ml), 2,4-디페닐-4-메틸-1-펜텐 14.8몰(1145.9ml), 톨루엔 2400ml를 10.0L의 반응기 내에 투입하고, 90℃로 240mmol의 과산화벤조일을 첨가하여 6시간 반응시켰다. 중합 반응을 냉각에 의해 정지시킨 후, 실온에서 반응 혼합액을 대량의 헥산에 투입하여 중합체를 석출시켰다. 얻어진 중합체를 헥산으로 세정하고, 여과 분별, 건조, 칭량 하여 공중합체 A 1392.6g(수율: 40.5wt%)을 얻었다. 3.2 mol (926.5 ml) of dimethyloltricyclodecane diacrylate, 8.0 mol (1814.1 ml) of isobornyl methacrylate, 4.8 mol (645.5 ml) of 2-hydroxypropyl methacrylate, 2,4-diphenyl-4 14.8 mol (1145.9 ml) of methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 캜 to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain 1392.6 g of Copolymer A (yield: 40.5 wt%).
얻어진 공중합체 A의 Mw는 8950, Mn은 3470, Mw/Mn은 2.58이었다. 13C-NMR, 1H-NMR 분석 및 원소 분석을 함으로써, 공중합체 A는 디메틸올트리시클로데칸디아크릴레이트 유래의 구조단위를 합계 18.2몰%, 이소보닐메타크릴레이트 유래의 구조단위를 합계 51.1몰%, 2-하이드록시프로필메타크릴레이트 유래의 구조단위를 30.7몰% 함유하고 있었다. 또한 2,4-디페닐-4-메틸-1-펜텐 유래의 구조의 말단기는 디메틸올트리시클로데칸디아크릴레이트, 이소보닐메타크릴레이트, 2-하이드록시프로필메타크릴레이트 및 2,4-디페닐-4-메틸-1-펜텐의 총량에 대하여 8.3몰% 존재하고 있었다. Mw of the obtained copolymer A was 8950, Mn was 3470, and Mw / Mn was 2.58. By carrying out 13 C-NMR, 1 H-NMR analysis and elemental analysis, copolymer A totaled 18.2 mol% of structural units derived from dimethyloltricyclodecane diacrylate, and 51.1 of structural units derived from isobornyl methacrylate. 30.7 mol% of structural units derived from mol% and 2-hydroxypropyl methacrylate were contained. Moreover, the terminal group of the structure derived from 2, 4- diphenyl-4-methyl-1- pentene is dimethylol tricyclodecane diacrylate, isobornyl methacrylate, 2-hydroxypropyl methacrylate, and 2, 4- 8.3 mol% existed with respect to the total amount of diphenyl-4-methyl-1-pentene.
공중합체 A는 톨루엔, 크실렌, THF, 디클로로에탄, 디클로로메탄, 클로로포름에 가용이며, 겔의 생성은 인정되지 않았다. 또한 공중합체 A의 캐스트 필름은 탁함이 없는 투명한 필름이었다. Copolymer A is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer A was a transparent film with no haze.
공중합체 A를 각종 측정 조건에 의해 경화 시트로 하였다. 경화 시트를 잘라내 얻은 시료에 대하여, 광학특성, 흡수율, 열중량 감소량, 내열변색성 및 내용제성의 측정을 실시하였다. Copolymer A was made into the hardened sheet by various measurement conditions. About the sample obtained by cutting out the hardened sheet, the optical characteristic, water absorption, the amount of thermogravimetry reduction, heat discoloration resistance, and solvent resistance were measured.
그 결과, 선팽창계수:91ppm/℃, 흡수율:0.98%, 내용제성:○이었다. As a result, the coefficient of linear expansion was 91 ppm / 占 폚, the absorption rate was 0.98%, and the solvent resistance was ○.
또한 TMA 측정 결과, 연화온도는 300℃ 이상이었다. TGA 측정 결과, 300℃에서의 중량 감소량은 1.8wt%, 내열변색성은 ◎이었다. Moreover, the softening temperature was 300 degreeC or more as a result of TMA measurement. As a result of TGA measurement, the weight loss at 300 ° C. was 1.8 wt% and the heat discoloration resistance was?.
또한 공중합체 A의 굴절률을 측정한 결과, 경화 후의 굴절률(589nm):1.520, 습열 시험 후의 굴절률(589nm):1.514이었다. Moreover, as a result of measuring the refractive index of copolymer A, it was the refractive index (589 nm) after hardening: 1.520, and the refractive index (589 nm) after wet-heat test: 1.514.
또한 밀착성 시험에서 잔존한 매스눈금의 개수를 센 결과, 100개의 매스눈금이 빠짐없이 기판상에 남아있는 것이 확인되었다. In addition, as a result of counting the number of remaining mass scales in the adhesion test, it was confirmed that 100 mass scales remained on the substrate without missing.
(실시예 2∼13 및 비교예 1∼6)(Examples 2 to 13 and Comparative Examples 1 to 6)
각종 2관능 아크릴레이트류, 단관능 (메타)아크릴레이트류를 사용해서 표 1에 나타내는 원료 조성으로 실시예 1과 동일하게 해서 중합하였다. It superposed | polymerized similarly to Example 1 using the raw material composition shown in Table 1 using various bifunctional acrylates and monofunctional (meth) acrylates.
반응에 사용한 원료의 사용량을 표 1 및 2에, 공중합체 및 그 경화물의 시험 결과를 표 3 및 4에 나타낸다. 특별히 언급하지 않는 한, 그 밖의 반응 조건 및 측정 조건은 실시예 1과 같다. 표 1에 있어서, 원료 사용량은 몰 및 중량(g)으로 표시하는데, 기재 형식은 몰/g으로 하였다. Tables 1 and 2 show the amounts of the raw materials used for the reaction, and test results of the copolymers and the cured products thereof are shown in Tables 3 and 4. Unless otherwise mentioned, other reaction conditions and measurement conditions are the same as Example 1. In Table 1, the amount of raw materials used is expressed in moles and weight (g), but the substrate format is set to moles / g.
표에서 사용한 약호를 이하에 나타낸다. The symbol used by the table | surface is shown below.
DMTCD: 디메틸올트리시클로데칸디아크릴레이트(c) DMTCD: Dimethylol tricyclodecane diacrylate (c)
BDDA: 1,4-부탄디올디아크릴레이트(c) BDDA: 1,4-butanediol diacrylate (c)
HOP: 2-하이드록시프로필메타크릴레이트(b) HOP: 2-hydroxypropyl methacrylate (b)
HO: 2-하이드록시에틸메타크릴레이트(b) HO: 2-hydroxyethyl methacrylate (b)
CD570: 부분 에톡시화 2-하이드록시에틸메타크릴레이트(b) CD570: partially ethoxylated 2-hydroxyethyl methacrylate (b)
IBOMA: 이소보닐메타크릴레이트(a) IBOMA: isobornyl methacrylate (a)
DCPM: 디시클로펜타닐메타크릴레이트(a) DCPM: Dicyclopentanyl methacrylate (a)
DCPA: 디시클로펜타닐아크릴레이트(a) DCPA: dicyclopentanyl acrylate (a)
αMSD: 2,4-디페닐-4-메틸-1-펜텐(d) αMSD: 2,4-diphenyl-4-methyl-1-pentene (d)
DDME: n-도데실메르캅탄 DDME: n-dodecyl mercaptan
MMA: 메틸메타크릴레이트 MMA: Methyl methacrylate
DCP-A; 트리시클로데칸디메탄올디아크릴레이트(쿄에이샤카가쿠 가부시키가이샤 제품) DCP-A; Tricyclodecane dimethanol diacrylate (Kyoeisha Kagaku Co., Ltd. product)
M-600A; 2-하이드록시-3-페녹시프로필아크릴레이트(에폭시에스테르 M-600A: 쿄에이샤카가쿠 가부시키가이샤 제품) M-600A; 2-hydroxy-3-phenoxypropyl acrylate (epoxy ester M-600A: manufactured by Kyoeisha Chemical Co., Ltd.)
3EG-A; 트리에틸렌글리콜디아크릴레이트(라이트 아크릴레이트 3EG-A: 쿄에이샤카가쿠 가부시키가이샤 제품) 3EG-A; Triethylene glycol diacrylate (light acrylate 3EG-A: product of Kyoeisha Chemical Co., Ltd.)
FA-513AS; 디시클로펜타닐아크릴레이트(히타치카세이코교 가부시키가이샤 제품) FA-513AS; Dicyclopentanyl acrylate (made by Hitachi Kasei Co., Ltd.)
FA-129AS; 노난디올디아크릴레이트(히타치카세이코교 가부시키가이샤 제품) FA-129AS; Nonandiol diacrylate (Hitachika Seiko Co., Ltd. product)
SR205; 트리에틸렌글리콜디메타크릴레이트(Sartomer-SR205: Sartomer사 제품) SR205; Triethylene glycol dimethacrylate (Sartomer-SR205: product of Sartomer)
EG; 에틸렌글리콜디메타크릴레이트(라이트 에스테르 EG; 쿄에이샤카가쿠 가부시키가이샤 제품) EG; Ethylene glycol dimethacrylate (light ester EG; product of Kyoeisha Chemical Co., Ltd.)
MEK-SD; 메틸에틸케톤 분산형 콜로이달 실리카(실리카 함량 30중량%, 평균 입자경 10∼20nm, 스노텍스 MEK-SD-(1); 닛산카가쿠 가부시키가이샤 제품) MEK-SD; Methyl ethyl ketone dispersed colloidal silica (30 wt% silica, average particle size 10-20 nm, Snowtex MEK-SD- (1); manufactured by Nissan Kagaku Co., Ltd.)
MEK-ST-MS; 메틸에틸케톤 분산형 콜로이달 실리카(실리카 함량 35wt%, 평균 입경 17∼23nm, MEK 용매, 스노텍스 MEK-ST-MS; 닛산카가쿠 가부시키가이샤 제품) MEK-ST-MS; Methyl ethyl ketone dispersed colloidal silica (silica content 35wt%, average particle size 17-23nm, MEK solvent, SNO-TEX MEK-ST-MS; manufactured by Nissan Kagaku Co., Ltd.)
MEK-ST-L; 메틸에틸케톤 분산형 콜로이달 실리카(실리카 함량 30wt%, 평균 입경 40∼50nm, MEK 용매, 스노텍스 MEK-ST-L; 닛산카가쿠 가부시키가이샤 제품) MEK-ST-L; Methylethylketone dispersed colloidal silica (silica content 30wt%, average particle size 40-50nm, MEK solvent, Snowtex MEK-ST-L; manufactured by Nissan Kagaku Co., Ltd.)
SC1050; 메틸에틸케톤 분산형 콜로이달 실리카(평균 입경 0.2∼0.3㎛, MEK 용매, 실리카 함량 65wt%, SC1050-MMA; 가부시키가이샤 아드마텍스(ADMATECHS) 제품) SC1050; Methyl ethyl ketone dispersed colloidal silica (average particle diameter 0.2-0.3 µm, MEK solvent, silica content 65 wt%, SC1050-MMA; manufactured by ADMATECHS)
AO-60; 산화 방지제(아데카 스탭 AO-60; 가부시키가이샤 아데카 제품)AO-60; Antioxidant (adeca staff AO-60; made by Adeka)
퍼부틸 O; t-부틸퍼옥시-2-에틸헥사네이트(니혼유시 가부시키가이샤 제품) Perbutyl O; t-butylperoxy-2-ethylhexanate (made by Nippon Oil Industries, Ltd.)
이르가큐어 184; 1-하이드록시-시클로헥실-페닐-케톤(치바·스페셜티·케미칼즈사 제품) Irgacure 184; 1-hydroxy cyclohexyl phenyl ketone (product of Chiba specialty chemicals company)
표 4에서 G는 겔화한 것을 나타내고, 표 4, 표 8에서 NM은 측정 불가를 나타낸다. 표 3∼6의 겔 생성에 있어서 ○은 있음을, X는 없음을 나타낸다. In Table 4, G shows gelation, and in Table 4 and Table 8, NM shows not measurable. In the gel formation of Tables 3 to 6, ○ is present and X is not present.
(합성예 1)Synthesis Example 1
실시예 1과 마찬가지로 해서 공중합체 A를 얻었다. Copolymer A was obtained in the same manner as in Example 1.
(합성예 2)Synthesis Example 2
1,4-부탄디올디아크릴레이트 4.8몰(950.4g), 디시클로펜타닐메타크릴레이트 6.4몰(922.7g), 2-하이드록시프로필메타크릴레이트 4.8몰(692.2g), 2,4-디페닐-4-메틸-1-펜텐 4.8몰(1135g), 톨루엔 2400ml를 10.0L의 반응기 내에 투입하고, 90℃로 240mmol의 과산화벤조일을 첨가하여 6시간 반응시켰다. 중합 반응을 냉각에 의해 정지시킨 후, 실온에서 반응 혼합액을 대량의 헥산에 투입하여 중합체를 석출시켰다. 얻어진 중합체를 헥산으로 세정하고, 여과 분별, 건조, 칭량하여 공중합체 B를 얻었다. 4.8 mole (950.4 g) of 1,4-butanediol diacrylate, 6.4 mole (922.7 g) of dicyclopentanyl methacrylate, 4.8 mole (692.2 g) of 2-hydroxypropyl methacrylate, 2,4-diphenyl- 4.8 mol (1135 g) of 4-methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain Copolymer B.
얻어진 공중합체 B의 Mw는 12500, Mn은 3640, Mw/Mn은 3.43이었다. 13C-NMR, 1H-NMR 분석 및 원소 분석을 함으로써, 공중합체 B는 1,4-부탄디올디아크릴레이트 유래의 구조단위를 합계 27.8몰%, 디시클로펜타닐메타크릴레이트 유래의 구조단위를 합계 27.8몰%, 2-하이드록시프로필메타크릴레이트 유래의 구조단위를 41.6몰% 함유하고 있었다. 또한 2,4-디페닐-4-메틸-1-펜텐 유래의 구조의 말단기는 1,4-부탄디올디아크릴레이트, 디시클로펜타닐메타크릴레이트, 2-하이드록시프로필메타크릴레이트 및 2,4-디페닐-4-메틸-1-펜텐의 총량에 대하여 10.1몰% 존재하고 있었다. 또한 펜던트 아크릴레이트의 비율은 20.4몰%였다. Mw of the obtained copolymer B was 12500, Mn was 3640 and Mw / Mn was 3.43. By performing 13 C-NMR, 1 H-NMR analysis and elemental analysis, copolymer B totaled 27.8 mol% of structural units derived from 1,4-butanediol diacrylate and the total of structural units derived from dicyclopentanyl methacrylate. 27.8 mol% and 41.6 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. In addition, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4. 10.1 mol% was exist with respect to the total amount of -diphenyl-4-methyl-1-pentene. Moreover, the ratio of pendant acrylate was 20.4 mol%.
공중합체 B는 톨루엔, 크실렌, THF, 디클로로에탄, 디클로로메탄, 클로로포름에 가용이며, 겔의 생성은 인정되지 않았다. 또한 공중합체 B의 캐스트 필름은 탁함이 없는 투명한 필름이었다. Copolymer B is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer B was a transparent film with no haze.
(합성예 3)Synthesis Example 3
1,4-부탄디올디아크릴레이트 5몰(990g), 디시클로펜타닐메타크릴레이트 1몰(144.2g), 2-하이드록시프로필메타크릴레이트 4몰(576.8g), 2,4-디페닐-4-메틸-1-펜텐 5몰(1182g), 톨루엔 2400ml를 10.0L의 반응기 내에 투입하고, 90℃로 240mmol의 과산화벤조일을 첨가하여 6시간 반응시켰다. 중합 반응을 냉각에 의해 정지시킨 후, 실온에서 반응 혼합액을 대량의 헥산에 투입하여 중합체를 석출시켰다. 얻어진 중합체를 헥산으로 세정하고, 여과 분별, 건조, 칭량하여 공중합체 C를 얻었다. 5 mol (990 g) of 1,4-butanediol diacrylate, 1 mol (144.2 g) of dicyclopentanyl methacrylate, 4 mol (576.8 g) of 2-hydroxypropyl methacrylate, 2,4-diphenyl-4 5 mol (1182 g) of methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain Copolymer C.
얻어진 공중합체 C의 Mw는 9230, Mn은 3210, Mw/Mn은 2.88이었다. 13C-NMR, 1H-NMR 분석 및 원소 분석을 함으로써, 공중합체 C는 1,4-부탄디올디아크릴레이트 유래의 구조단위를 합계 45.6몰%, 디시클로펜타닐메타크릴레이트 유래의 구조단위를 합계 12.3몰%, 2-하이드록시프로필메타크릴레이트 유래의 구조단위를 42.1몰% 함유하고 있었다. 또한 2,4-디페닐-4-메틸-1-펜텐 유래의 구조의 말단기는 1,4-부탄디올디아크릴레이트, 디시클로펜타닐메타크릴레이트, 2-하이드록시프로필메타크릴레이트 및 2,4-디페닐-4-메틸-1-펜텐의 총량에 대하여 14.6몰% 존재하고 있었다. 또한 펜던트 아크릴레이트의 비율은 32.6몰%였다. Mw of the obtained copolymer C was 9230, Mn was 3210 and Mw / Mn was 2.88. By performing 13 C-NMR, 1 H-NMR analysis and elemental analysis, copolymer C totaled 45.6 mol% of structural units derived from 1,4-butanediol diacrylate and the structural units derived from dicyclopentanyl methacrylate. 12.3 mol% and 42.1 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. In addition, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4. 14.6 mol% was present relative to the total amount of -diphenyl-4-methyl-1-pentene. Moreover, the ratio of pendant acrylate was 32.6 mol%.
공중합체 C는 톨루엔, 크실렌, THF, 디클로로에탄, 디클로로메탄, 클로로포름에 가용이며, 겔의 생성은 인정되지 않았다. 또한 공중합체 C의 캐스트 필름은 탁함이 없는 투명한 필름이었다. Copolymer C is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer C was a transparent film with no haze.
(합성예 4∼15 및 합성예 16∼20)(Synthesis Examples 4-15 and Synthesis Examples 16-20)
합성예 1과 동일한 방법을 이용해서, 아크릴레이트류의 종류 및 사용량을 표 1∼2에 나타내는 배합으로 변화시켜 각종 공중합체를 합성하였다. 또한 합성예 1∼15는 실시예이고, 합성예 16∼20은 비교를 위한 합성예이다. 결과를 표 5∼8에 정리해서 나타낸다. By using the same method as in Synthesis Example 1, various copolymers were synthesized by changing the type and the amount of acrylate used in the formulations shown in Tables 1-2. Synthesis Examples 1-15 are Examples, and Synthesis Examples 16-20 are Synthesis Examples for comparison. The results are collectively shown in Tables 5-8.
(실시예 14∼38 및 비교예 7∼14)(Examples 14 to 38 and Comparative Examples 7 to 14)
합성예에서 합성한 각종 공중합체와, (메타)아크릴레이트류, 실리카 미립자 및 중합개시제 등의 첨가제를 표 9∼11에 나타내는 비율로 혼합하여 경화성 조성물을 얻었다. 다음으로 이 경화성 수지 조성물을 상기의 각종 시험방법에 의해 경화하여 성능평가를 행하였다. 성능평가 결과를 표 9∼11에 나타낸다. Various copolymers synthesized in the synthesis examples and additives such as (meth) acrylates, silica fine particles, and polymerization initiators were mixed in the ratios shown in Tables 9 to 11 to obtain a curable composition. Next, this curable resin composition was hardened by the above various test methods, and performance evaluation was performed. The performance evaluation results are shown in Tables 9-11.
표 5∼8에서, 성분(a)∼(c)의 숫자는 사용량(몰)을 나타내고, 괄호 안의 숫자는 아크릴레이트류 중의 몰%이며, DMP의 숫자는 사용량(몰)을 나타내고, 괄호 안의 숫자는 아크릴레이트류의 총량에 대한 몰%이다. 또한 그 밖의 모노머 성분으로서 MMA를 사용할 경우에는 이것을 아크릴레이트류로서 계산한다. 또한 각 성분의 함유량은 공중합체에 존재하는 각 성분에 유래하는 구조단위의 존재비(몰비)인데, 각각 상기 식(1)∼(5)로 계산된다. 또한 그 밖의 모노머 성분으로서 MMA를 사용할 경우에는 이것을 아크릴레이트류에 유래하는 구조단위로서 계산한다. In Tables 5 to 8, the numbers of components (a) to (c) indicate the amount of use (moles), the numbers in parentheses indicate the mole percent in the acrylates, the number of DMP indicates the amount of use (moles), and the numbers in parentheses. Is mol% with respect to the total amount of acrylates. In addition, when MMA is used as another monomer component, it is calculated as acrylates. In addition, content of each component is an abundance ratio (molar ratio) of the structural unit derived from each component which exists in a copolymer, Computed by said Formula (1)-(5), respectively. In addition, when MMA is used as another monomer component, it is calculated as a structural unit derived from acrylates.
또한 표 9∼11에서, (C)성분의 실리카의 중량은 용제분을 제외한 고형분 중량이다. 내히트사이클성 및 내습성의 평가에 있어서 ○은 박리 없음을 나타내고, X는 박리를 나타낸다. In addition, in Tables 9-11, the weight of the silica of (C) component is the weight of solid content except a solvent powder. In the evaluation of heat cycle resistance and moisture resistance, o indicates no peeling, and X indicates peeling.
Claims (12)
2,4-디페닐-4-메틸-1-펜텐(d) 유래의 구조단위의 도입량이, 하기 식(1)로 표시되는 몰분율(Md)로서 0.02∼0.35인 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체.
Md=(d)/[(a)+(b)+(c)+(d)] (1)
여기서 (a), (b), (c) 및 (d)는 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)에 유래하는 구조단위, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)에 유래하는 구조단위, 2관능 (메타)아크릴산에스테르(c)에 유래하는 구조단위 및 2,4-디페닐-4-메틸-1-펜텐(d)에 유래하는 구조단위의 몰수를 나타낸다.The method of claim 1,
The amount of introduction of the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene ( d ) is 0.02 to 0.35 as the mole fraction (M d ) represented by the following formula (1). (Meth) acrylic acid ester copolymer.
M d = (d) / [(a) + (b) + (c) + (d)] (1)
Here (a), (b), (c) and (d) are a monofunctional (meth) acrylic acid ester which has a structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and an alcoholic hydroxyl group ( The number of moles of the structural unit derived from b), the structural unit derived from bifunctional (meth) acrylic acid ester (c), and the structural unit derived from 2, 4- diphenyl-4-methyl-1- pentene (d) are shown. .
2관능 (메타)아크릴산에스테르(c) 유래의 반응성의 (메타)아크릴레이트기(c1)의 도입량이, 하기 식(2)로 표시되는 몰분율(Mc1)로서 0.05∼0.5인 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체.
Mc1=(c1)/[(a)+(b)+(c)] (2)
여기서 식 중의 (c1)은 측쇄에 2관능 (메타)아크릴레이트기(c1)를 함유하는 구조단위의 몰수를 나타낸다. The method of claim 1,
The solubility of the reactive (meth) acrylate group (c1) derived from the bifunctional (meth) acrylic acid ester (c) is 0.05 to 0.5 as the mole fraction (M c1 ) represented by the following formula (2). Polyfunctional (meth) acrylic acid ester copolymer.
M c1 = (c1) / [(a) + (b) + (c)] (2)
Here, (c1) shows the number-of-moles of the structural unit containing a bifunctional (meth) acrylate group (c1) in a side chain.
상기 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)가 이소보닐메타크릴레이트, 이소보닐아크릴레이트, 시클로헥실메타크릴레이트, 시클로헥실아크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트, 디시클로펜테닐옥시에틸메타크릴레이트 및 디시클로펜타닐메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 단관능 (메타)아크릴산에스테르인 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체. The method of claim 1,
Monofunctional (meth) acrylic acid ester (a) which has the said alicyclic structure is isobornyl methacrylate, isobonyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl At least one monofunctional (meth) selected from the group consisting of oxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate and dicyclopentanyl methacrylate A soluble polyfunctional (meth) acrylic acid ester copolymer characterized by the above-mentioned.
상기 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)가 2-하이드록시프로필메타크릴레이트, 2-하이드록시에틸메타크릴레이트 및 부분적으로 에톡시화된 2-하이드록시메타크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 알코올성 수산기를 가지는 (메타)아크릴산에스테르인 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체. The method of claim 1,
In the group wherein the monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group consists of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and partially ethoxylated 2-hydroxymethacrylate. It is (meth) acrylic acid ester which has 1 or more types of alcoholic hydroxyl groups selected, The soluble polyfunctional (meth) acrylic acid ester copolymer characterized by the above-mentioned.
상기 2관능 (메타)아크릴산에스테르(c)가, 시클로헥산디메탄올디아크릴레이트 및 디메틸올트리시클로데칸디아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 2관능 (메타)아크릴산에스테르인 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체. The method of claim 1,
Said bifunctional (meth) acrylic acid ester (c) is 1 or more types of bifunctional (meth) acrylic acid ester chosen from the group which consists of cyclohexane dimethanol diacrylate and dimethylol tricyclodecane diacrylate, It is characterized by the above-mentioned. Soluble polyfunctional (meth) acrylic acid ester copolymer.
2,4-디페닐-4-메틸-1-펜텐(d)을 2관능 (메타)아크릴산에스테르(c) 100중량부에 대하여 10∼500중량부 존재시키고, 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르(a)를 2∼55몰%, 알코올성 수산기를 가지는 단관능 (메타)아크릴산에스테르(b)를 2∼50몰% 및 2관능 (메타)아크릴산에스테르(c)를 96∼10몰% 함유하여 이루어지는 단량체 성분을 50∼200℃의 온도로 중합시키는 것을 특징으로 하는 가용성 다관능 (메타)아크릴산에스테르 공중합체의 제조방법. The method of claim 1,
10-500 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (d) is present based on 100 parts by weight of the bifunctional (meth) acrylic acid ester (c), and has a monofunctional (meth) having an alicyclic structure. 2 to 55 mol% of acrylic acid ester (a) and 2 to 50 mol% of monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group and 96 to 10 mol% of bifunctional (meth) acrylic acid ester (c) A method for producing a soluble polyfunctional (meth) acrylic acid ester copolymer, comprising polymerizing a monomer component containing at a temperature of 50 to 200 ° C.
(B)성분: 불포화 이중결합을 가지는 관능기를 1개 이상 가지며, 분자량이 1000 이하인 모노머, 및
(C)성분: 평균 입자경이 1∼100nm인 실리카 미립자
를 함유하는 것을 특징으로 하는 경화성 수지 조성물. (A) component: The soluble polyfunctional (meth) acrylic acid ester copolymer of Claim 1,
(B) component: Monomer which has one or more functional groups which have an unsaturated double bond, molecular weight is 1000 or less, and
(C) component: silica fine particles whose average particle diameter is 1-100 nm
Curable resin composition characterized by including the.
(A)성분 및 (B)성분의 합계에 대한 (A)성분의 배합량이 2∼83wt%, (B)성분의 배합량이 83∼2wt%, (C)성분의 배합량이 15∼90wt%인 것을 특징으로 하는 경화성 수지 조성물. The method of claim 8,
The compounding quantity of (A) component with respect to the sum total of (A) component and (B) component is 2-83 wt%, the compounding quantity of (B) component is 83-2 wt%, and the compounding quantity of (C) component is 15-90 wt% Curable resin composition characterized by the above-mentioned.
상기 B 성분이, 지환식 구조를 가지는 단관능 (메타)아크릴산에스테르 및 2관능 (메타)아크릴산에스테르에서 선택되는 1종 이상의 (메타)아크릴산에스테르인 것을 특징으로 하는 경화성 수지 조성물. The method of claim 8,
Curable resin composition characterized by the above-mentioned B component being 1 or more types of (meth) acrylic acid ester chosen from monofunctional (meth) acrylic acid ester and bifunctional (meth) acrylic acid ester which have alicyclic structure.
또한 (D)성분으로서 광중합 개시제를 포함하는 것을 특징으로 하는 경화성 수지 조성물. The method of claim 8,
Furthermore, curable resin composition containing a photoinitiator as (D) component.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010075685A JP5596390B2 (en) | 2010-03-29 | 2010-03-29 | Soluble polyfunctional (meth) acrylic acid ester copolymer having alcoholic hydroxyl group and method for producing the same |
| JPJP-P-2010-075685 | 2010-03-29 | ||
| JP2010207672A JP5444177B2 (en) | 2010-09-16 | 2010-09-16 | Curable composite composition and cured product thereof |
| JPJP-P-2010-207672 | 2010-09-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20110109938A true KR20110109938A (en) | 2011-10-06 |
| KR101790646B1 KR101790646B1 (en) | 2017-10-26 |
Family
ID=45026895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110027549A KR101790646B1 (en) | 2010-03-29 | 2011-03-28 | Soluble polyfunctional (meth)acrylic ester copolymer, and method for production thereof, curable resin composition and cured product |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101790646B1 (en) |
| CN (1) | CN102351978B (en) |
| TW (1) | TWI605066B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130074760A (en) * | 2011-12-26 | 2013-07-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Curable resin composition, cured article thereof, and optical material |
| CN103492433A (en) * | 2011-02-14 | 2014-01-01 | 株式会社Lg化学 | Solventless composition and method for preparing same |
| KR20150139891A (en) * | 2013-03-29 | 2015-12-14 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Polyfunctional (meth)acrylic acid ester copolymer, and curable resin composition and cured product thereof |
| EP3962411A4 (en) * | 2019-05-03 | 2023-01-25 | Johnson & Johnson Surgical Vision, Inc. | High reactive index, high abbe compositions |
| US11708440B2 (en) | 2019-05-03 | 2023-07-25 | Johnson & Johnson Surgical Vision, Inc. | High refractive index, high Abbe compositions |
| US11795252B2 (en) | 2020-10-29 | 2023-10-24 | Johnson & Johnson Surgical Vision, Inc. | Compositions with high refractive index and Abbe number |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI664199B (en) * | 2014-12-26 | 2019-07-01 | 日商日鐵化學材料股份有限公司 | Terminally modified soluble polyfunctional vinyl aromatic copolymer, method for producing the same, hardening composition, hardened material, film, hardenable composite material, laminate, metal foil with resin, varnish for circuit board material, hardening Resin composition, resin film for forming optical waveguide, and optical waveguide |
| JP6600253B2 (en) * | 2015-12-25 | 2019-10-30 | 東京応化工業株式会社 | Permanent adhesive composition for image sensor, and bonding method and laminate using the same |
| JP6388185B1 (en) * | 2017-12-01 | 2018-09-12 | パナソニックＩｐマネジメント株式会社 | Paint composition |
| CN114516962B (en) * | 2020-11-19 | 2024-04-26 | 北京鼎材科技有限公司 | High light-transmitting photosensitive resin and color photosensitive resin composition using same |
| CN113943436B (en) * | 2021-09-29 | 2023-06-02 | 郑州大学 | Preparation method of solvent-resistant high-dielectric-constant insulating layer capable of being simply patterned |
| CN113917757B (en) * | 2021-11-26 | 2023-10-13 | 浙江精一新材料科技有限公司 | Light valve device containing liquid polymer with nonlinear structure, liquid polymer with nonlinear structure and preparation method thereof |
| CN115746648B (en) * | 2022-12-20 | 2024-03-15 | 长飞光纤光缆股份有限公司 | Low-friction self-lubricating control resin for air-blown optical cable, preparation method thereof and optical cable |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716102B1 (en) | 1994-06-24 | 2002-02-06 | Seiko Epson Corporation | Transparent plastic material, optical article made therefrom, and production process |
| JP2003306619A (en) * | 2002-04-16 | 2003-10-31 | Nippon Kayaku Co Ltd | Photosensitive resin composition for hard-coating agent and film having cured skin comprising the same |
| DE10237576A1 (en) * | 2002-08-16 | 2004-02-26 | Bayer Ag | Aqueous binder dispersions as coating agents |
| US7312290B2 (en) * | 2004-09-24 | 2007-12-25 | General Electric Company | Curable formulations, cured compositions, and articles derived thereform |
| JP4970107B2 (en) | 2007-03-29 | 2012-07-04 | 新日鐵化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer and method for producing the same |
-
2011
- 2011-03-23 TW TW100109888A patent/TWI605066B/en active
- 2011-03-28 KR KR1020110027549A patent/KR101790646B1/en active IP Right Grant
- 2011-03-29 CN CN201110198689.XA patent/CN102351978B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492433A (en) * | 2011-02-14 | 2014-01-01 | 株式会社Lg化学 | Solventless composition and method for preparing same |
| CN103492433B (en) * | 2011-02-14 | 2016-12-14 | 株式会社Lg化学 | solvent-free composition and preparation method thereof |
| US9765232B2 (en) | 2011-02-14 | 2017-09-19 | Lg Chem, Ltd. | Solventless composition and method for preparing the same |
| KR20130074760A (en) * | 2011-12-26 | 2013-07-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Curable resin composition, cured article thereof, and optical material |
| KR20150139891A (en) * | 2013-03-29 | 2015-12-14 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Polyfunctional (meth)acrylic acid ester copolymer, and curable resin composition and cured product thereof |
| EP3962411A4 (en) * | 2019-05-03 | 2023-01-25 | Johnson & Johnson Surgical Vision, Inc. | High reactive index, high abbe compositions |
| US11667742B2 (en) | 2019-05-03 | 2023-06-06 | Johnson & Johnson Surgical Vision, Inc. | Compositions with high refractive index and Abbe number |
| US11708440B2 (en) | 2019-05-03 | 2023-07-25 | Johnson & Johnson Surgical Vision, Inc. | High refractive index, high Abbe compositions |
| US11958923B2 (en) | 2019-05-03 | 2024-04-16 | Johnson & Johnson Surgical Vision, Inc. | Compositions with high refractive index and abbe number |
| US11795252B2 (en) | 2020-10-29 | 2023-10-24 | Johnson & Johnson Surgical Vision, Inc. | Compositions with high refractive index and Abbe number |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102351978A (en) | 2012-02-15 |
| CN102351978B (en) | 2016-03-02 |
| TW201200532A (en) | 2012-01-01 |
| TWI605066B (en) | 2017-11-11 |
| KR101790646B1 (en) | 2017-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5281710B2 (en) | Curable resin composition, cured product and optical material | |
| KR20110109938A (en) | Soluble polyfunctional (meth)acrylic ester copolymer, and method for production thereof, curable resin composition and cured product | |
| KR101798206B1 (en) | Curable resin composition and cured product thereof | |
| EP2275459B1 (en) | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition | |
| JP5841835B2 (en) | Curable resin composition, cured product and optical article | |
| JP6525867B2 (en) | Curable resin composition, cured product and optical article | |
| JP5444177B2 (en) | Curable composite composition and cured product thereof | |
| KR102174272B1 (en) | Polyfunctional (meth)acrylic acid ester copolymer, and curable resin composition and cured product thereof | |
| JP5502791B2 (en) | Curable resin composition, cured product and optical material | |
| TWI529182B (en) | Acluble polyfunctional (meth) acrylate copolymer having an alicyclic structure, a hardened resin composition and a hardened product | |
| JP5485205B2 (en) | Soluble polyfunctional (meth) acrylic acid ester copolymer having alicyclic structure, curable resin composition, cured product, and optical material | |
| JP5457160B2 (en) | Soluble polyfunctional (meth) acrylic acid ester copolymer having alicyclic structure and method for producing the same | |
| JP5596390B2 (en) | Soluble polyfunctional (meth) acrylic acid ester copolymer having alcoholic hydroxyl group and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |